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Active Wetlands the use of chemical amendments to intercept phosphate runoffs in agricultural catchments
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1 92 Active Wetlands the use of chemical amendments to intercept phosphate runoffs in agricultural catchments Final report of the Active Wetlands Interreg IVA project Risto Uusitalo, Aaro Närvänen, Kimmo Rasa, Tapio Salo, Jari Koskiaho, Markku Puustinen, Anne Brax, Elina Erkkilä, Sampsa Vilhunen, Päivi Joki-Heiskala, Antti Kaseva, Eemeli Huhta, Piia Leskinen, Martin Liira, Egle Saaremäe, Morten Poolakese, Toomas Tamm, Kuno Kasak, Indrek Talpsep, Ivar Tamm
2 ISBN (Printed version) ISBN (Electronic version) ISSN Copyright: MTT Authors: Risto Uusitalo, Aaro Närvänen, Kimmo Rasa, Tapio Salo, Jari Koskiaho, Markku Puustinen, Anne Brax, Elina Erkkilä, Sampsa Vilhunen, Päivi Joki-Heiskala, Antti Kaseva, Eemeli Huhta, Piia Leskinen, Martin Liira, Egle Saaremäe, Morten Poolakese, Toomas Tamm, Kuno Kasak, Indrek Talpsep, Ivar Tamm Distribution and sale: MTT, Jokioinen Printing year: 2013 Cover picture: Morten Poolakese
3 Active Wetlands maatalouden valumavesien fosforin sitominen kemikaalilisäyksen avulla Risto Uusitalo 1), Aaro Närvänen 1), Kimmo Rasa 1), Tapio Salo 1), Jari Koskiaho 2), Markku Puustinen 2), Anne Brax 3), Elina Erkkilä 3), Sampsa Vilhunen 3), Päivi Joki-Heiskala 4), Antti Kaseva 5), Eemeli Huhta 5), Piia Leskinen 5), Egle Saaremäe 6), Morten Poolakese 6), Toomas Tamm 6), Martin Liira 7), Kuno Kasak 8), Indrek Talpsep 8), Ivar Tamm 8) 1) MTT, FI Jokioinen, 2) Suomen Ympäristökeskus, FI Helsinki, 3) WWF-Finland, FI Helsinki, 4) Paimionjoki-yhdistys ry, FI Somero, 5) Turun ammattikorkeakoulu, FI Turku, 6) Estonian University of Life Sciences, EE Tartu, 7) University of Tartu, EE Tartu, 8) Estonian Fund for Nature, EE Tartu, Tiivistelmä Suomessa ja Virossa tutkittiin mahdollisuuksia tehostaa liuenneen fosforin pidättymistä pieniin kosteikkoihin ja pelto-ojiin, jotka ovat yleensä huonoja pysäyttämään vesistöjä rehevöittävää liuennutta fosforia. Hankkeessa tehtiin kenttäkokeita 20 paikalla joko annostelemalla veteen liukenevaa rautasulfaattia ojaveteen tai ohjaamalla valumavesiä kiinteiden, fosforia pidättävien materiaalien läpi. Käytimme kokeissa kahdentyyppisiä kiinteitä aineita, rautahydroksideja sisältäviä Sachtofer PR -rakeita ja runsaasti kalsiumia sisältävää, palavakiven poltosta jätteeksi jäävää mursketta. Kun menetelmät toimivat moitteettomasti, vedestä saatiin sidottua liuennutta fosforia hyvin tehokkaasti. Rautasulfaatti muodostaa veteen liuetessaan fosforin kanssa yhdisteitä, jotka eivät ole enää leville ja vesikasveille käyttökelpoisessa muodossa. Näin fosforin rehevöittävä vaikutus pienenee, vaikka yhdisteet jäisivätkin vesiympäristöön. Rautasulfaatin annostelulaitteet vaativat toiminnan seuraamista ja kemikaalin lisäämistä. Paras kustannus-hyötysuhde saavutetaan, kun valumaveden fosforipitoisuus on korkea, jolloin fosforikilon sitominen rauta-fosfori -yhdisteiksi tulee maksamaan vain muutamia kymmeniä euroja. Ojissa, joissa liuenneen fosforin pitoisuus oli matala, kustannukset kymmenkertaistuivat. Tutkitut kiinteät fosforinpidättäjät ovat periaatteessa turvallisempia ja helpompia liukoisen fosforin poistajia kuin veteen liukenevat kemikaalit. Perustamisen jälkeen rakenteita ei tarvitse juurikaan huoltaa, minkä lisäksi fosforin pidättäminen kiinteään aineeseen mahdollistaa sen keräämisen pois vesiympäristöstä ja siten myös kierrätyksen takaisin pelloille. Tässä hankkeessa tutkitut rakenteet kuitenkin toimivat toivotulla teholla vain hetken aikaa. Kokeiden aikana muodostuneet oikovirtaukset ja mm. leväkasvu heikensivät lopputulosta. Molemmat prosessit estivät veden ja pidättäjäaineiden välisen kontaktin ja heikensivät fosforin pidättymistä. Uudet, aktiiviset vesienkäsittelymenetelmät ovat parhaimmillaan hyviä apukeinoja fosforikuorman vähentämisessä. Ne kannattaa sijoittaa paikkoihin, joissa esiintyy todennetusti korkeita liuenneen fosforin pitoisuuksia. Kuitenkin näemme selviä kehitystarpeita, jotta nämä menetelmät saadaan toimimaan luotettavasti ja turvallisesti. Haastattelututkimuksiin osallistuneilla viljelijöillä oli pääsääntöisesti myönteinen asenne ravinnekulkeumien vähentämiseen, myös kemiallisilla menetelmillä. Avainsanat: fosfori, kosteikot, kemiallinen käsittely, rautasulfaatti, rautaoksidit, palavakivi, saostuminen, pidättyminen, fosfaatin sitominen, maatalous, valumavedet, rehevöityminen MTT REPORT 92 3
4 Active Wetlands the use of chemical amendments to intercept phosphate runoffs in agricultural catchments Risto Uusitalo 1), Aaro Närvänen 1), Kimmo Rasa 1), Tapio Salo 1), Jari Koskiaho 2), Markku Puustinen 2), Anne Brax 3), Elina Erkkilä 3), Sampsa Vilhunen 3), Päivi Joki-Heiskala 4), Antti Kaseva 5), Eemeli Huhta 5), Piia Leskinen 5), Egle Saaremäe 6), Morten Poolakese 6), Toomas Tamm 6), Martin Liira 7), Kuno Kasak 8), Indrek Talpsep 8), Ivar Tamm 8) 1) MTT Agrifood Research, FI Jokioinen, 2) Finnish Environment Institute, FI Helsinki, 3) WWF-Finland, FI Helsinki, 4) Paimionjoki-yhdistys ry, FI Somero, 5) Turku University of Applied Sciences, FI Turku, 6) Estonian University of Life Sciences, EE Tartu, 7) University of Tartu, EE Tartu, 8) Estonian Fund for Nature, EE Tartu, elfond.ee Abstract In this project conducted in Finland and Estonia we studied different applications that can be used to boost the retention of dissolved phosphorus (P) in agricultural wetlands and field ditches. Wetlands are usually inefficient in retaining the dissolved P component that has a profound effect on eutrophication in surface waters, such as nuisance growth of algae and macrophyte plant species. The work included field-scale studies at twenty test sites where precipitation of dissolved P was obtained by dosing ferric sulphate (a soluble metal salt) to water, or water was brought into contact with solid P sequester materials. We tested two different types of solid P retention materials: Sachtofer PR, a granulated product that contains iron hydroxides, and oil shale ash, which contains reactive calcium minerals. Testing revealed that dissolved P concentrations can be effectively reduced by the methods used when they work as intended. Ferric sulphate binds dissolved P in a form (Fe-P associations) that is no longer available for biological utilization by algae or other water biota, and thus decreases the eutrophying effects of the P load. The dosers used in administrating ferric sulphate to water, however, require maintenance and oversight, such as filling up the chemical storage and checking on the ph of the treated water. When applied at sites with a high dissolved P concentration, ferric sulphate proved to be very costefficient the cost of treating a kilogram of dissolved P was only in the tens of euros. At sites with a low dissolved P concentration, however, the cost of binding a kilogram of dissolved P in a non-bioavailable form was in the hundreds of euros. On the other hand, at their best, solid P sequester materials are maintenance-free after construction and allow for the collection of P out of the water system for possible recycling; however, they proved to work with poor efficiency when a long test period (up to several years) was concerned. Problems encountered with the solid P sequesters were associated with processes that inhibited contact between the water and the reactive surfaces of the materials. Consequently, the high P retention capacities of these materials were not realized in practice. Farmers generally had positive attitudes towards methods that reduce nutrient transports from soil to water, including the use of chemicals. Treating field runoffs to bind dissolved P is a viable and new option in nutrient mitigation that could be successfully used at the so-called hot-spots of P loading, i.e., at sites that produce higher dissolved P concentrations than the surrounding areas. The tested solutions should be further developed to ensure safe and efficient operation before they are recommended for practical water protection work. Keywords: phosphorus, wetlands, chemical amendments, ferric sulphate, iron oxides, oil shale, precipitation, adsorption, phosphate retention, agriculture, runoff, eutrophication 4 MTT REPORT 92
5 Contents 1 Introduction Phosphorus, wetlands and active measures Phosphorus and agriculture Phosphorus forms and eutrophication potential Wetlands and nutrient retention Chemical amendments to increase P retention in wetlands Project description and objectives Permissions and legislation Material and methods Selection of test sites Site surveys in Finland Site surveys in Estonia Selection criteria for the test sites Tested chemicals Ferric sulphate and its dosing Tests with solid P retention media Sampling and methods of water analyses Test set-ups at different sites Hovi wetland without chemical amendments Nautela tests with ferric sulphate Lake Nuutajärvi area tests with ferric sulphate River Paimiojoki area and Tammela tests with ferric sulphate Rahinge tests with ferric sulphate Ojainen tests with Sachtofer PR granules Rahinge tests with Sachtofer PR granules Rahinge tests with oilshale ash Interviews with farmers Interviews conducted in Finland Interviews conducted in Estonia Results Wetlands without chemical amendments Hovi constructed wetland Snapshots of P concentrations in other wetlands Precipitation of P with ferric sulphate Nautela tests Nuutajärvi tests Paimionjoki and Tammela tests Rahinge tests Solid P retention materials Ojainen tests with Sachtofer PR granules Rahinge tests with Sachtofer PR granules Rahinge tests with oilshale ash Disturbances and risks associated with the use of chemicals Poll of farmers Interviews conducted in Finland Interviews conducted in Estonia Discussion Phosphorus retention in wetlands without chemical treatments Precipitation of dissolved P by ferric sulphate Solid P retention media Communication of the Active Wetlands project Conclusions References...52 MTT REPORT 92 5
6 1 Introduction 1.1 Phosphorus, wetlands and active measures Phosphorus and agriculture Phosphorus (P) is one of the major elements that plants need for growth and seed production. A century ago soils were largely deficient in this essential nutrient and P applications clearly increased yields of cultivated plants. Between the 1950s and the late 1990s, however, applications brought increasingly larger surpluses to an average field hectare in many industrialized countries. For example, P use in Finland peaked in the late 1980s and at that time P inputs to an average field hectare were about 30 kg larger than P removal by harvested crops. It was estimated by Saarela (2002) that P applications to Finnish agricultural soils have led to doubling the total P content of the plough layer of agricultural fields during the last one hundred years. As a result of increasing the P content of agricultural soils, P transport from land to water has increased over time, as an increase in soil P status translates into higher P concentrations in runoff and drainage waters (e.g., Heckrath et al., 1995; Uusitalo and Jansson, 2002). To cope with the eutrophication of surface waters, the EU Water Framework Directive (Directive 2000/60/EC) targets the restoration or enhancement of the chemical and ecological status of water bodies, and for this purpose the main nutrient sources need mitigation. Because agriculture is currently considered as a major contributor to P loading of surface waters in all countries around the Baltic Sea (see HELCOM, 2009), agricultural sources need to be covered in mitigation plans. When the soil P status is high, a reduction in P transport from the soil to water would require lowering the soil P content. In practice, P applications to these fields should be withheld, or at least greatly reduced so that the P balance (P inputs less P outputs) would be negative (i.e., more P is harvested from the field than added with fertilizers and animal manure). Turning the surplus P applications into balanced applications, or in high P soils into negative P balances, is especially problematic in areas where animal husbandry has increased in intensity. Because animal farms have concentrated in certain regions, and feed for domestic animals is increasingly imported from outside these regions, there is a continuous surplus of nutrient balances in animal farms and areas where they are concentrated. Even when P inputs to agricultural soils can be reduced, it takes considerable time to reduce the soil P stock and thus affect P losses to water Phosphorus forms and eutrophication potential Phosphorus in runoff or drainage waters is operationally defined as particulate and dissolved forms. Particulate P is associated with sediment matter, whereas the pool of dissolved P includes orthophosphate and P of dissolved organic molecules. The dissolved fraction is commonly taken to be totally available for biological utilization (Ekholm and Krogerus, 2003), but the bioavailability of particulate P is lower. Earlier studies on runoff and drainage waters from Finnish clay soils have suggested that, depending on the soil P status, 20 50% of particulate P may in a short term turn into dissolved form (Uusitalo et al., 2003). Because particulate P often makes up a major proportion of the total P in agricultural runoff, both forms may, however, substantially contribute to the eutrophication of receiving waters. The particulate and dissolved P pools continuously change as a result of changes in water chemistry and biological activity. The water chemistry-driven changes involve reactions such as a P release from a particulate pool (including bottom sediment) into dissolved pool, the retention of dissolved P to particle surfaces, and precipitation/dissolution reactions. The partitioning of P in particulate and dissolved pools is driven by changes in P concentration in water, ph, the reduction oxidation state of sediment and water, and concentrations of dissolved ions in water (i.e., ionic strength of water). In general, the retention of P on particle surfaces is increased with an increase in P concentration in water, a decrease in ph, the presence of dissolved oxygen, and an increase in ionic strength. Conversely, P solubilisation from particles to dissolved pool is increased at a low P concentration in water, a high ph, a low supply in dissolved oxygen, and at a low concentration of dissolved ions. The biological cycle, in turn, withdraws P from the solution phase and embeds it in living cells as storage compounds (e.g., inositol phosphates of plant seeds or polyphosphates of bacterial cells), as parts of cell 6 MTT REPORT 92
7 wall structures (phospholipids), as building blocks of nucleic acids (DNA, RNA), and as parts of cell energy storage systems (e.g., in mithocondria). Upon the death of plants and other organisms these phosphorus compounds are released into the surroundings and after decomposition may re-enter the biological and chemical cycles. Larger bursts of P from the biological compartment may occur as a result of frost and drought Wetlands and nutrient retention In pristine landscapes wetlands develop on sites where the water flow slows down before entering waterways. When the water flow calms down, particulate matter sedimentation occurs and algae, bacteria and higher plants may assimilate nutrients from water and sediment. Of the main water pollutants due to agricultural operations, that is, phosphorus and nitrogen (N), P may be retained in a wetland by deposition and assimilation. For N, the main sink is, however, the atmosphere where N ends up after the conversion of nitrate (NO 3 ) to nitrogen gas (N 2 ) by denitrifying bacteria. Nitrogen removal in wetlands is well established (e.g., Tanner et al., 2010), but studies on P removal from runoff and drainage water by wetlands show variable efficiencies (cf. Koskiaho et al., 2003; Tanner and Sukias, 2011). Biological accumulation of P in wetlands directly involves dissolved P only. Due to biological activity that is regulated by temperature, P assimilation in wetlands takes place during the warm season, whereas a variable part of the accumulated nutrients are re-released into water from decaying biomass during the cold season. As a result, in the warm season and low-flow periods wetlands act as nutrient sinks, but commonly turn into nutrient sources in the cold season and high-flow periods. During an annual cycle the net accumulation of phosphorus may take place if there is net sediment accumulation and/or if the roots of wetland plants are permanently buried in the sediment and only undergo partial and slow decomposition. However, studies on established wetlands suggest that the net P accumulation over several years may in most cases be of minor importance (see Tanner and Sukias, 2011). Particulate P accumulation in wetlands takes place as a result of sediment deposition which thus requires that the water flow calms down. It is the small soil particles that contain clearly higher P concentrations than larger ones (e.g., Sharpley, 1985; Uusitalo et al., 2001), but in a small wetland fine-grained particles may not settle at all or flow peaks may cause resuspension of settled particles and transport them further downstream. Especially in landscapes with fine soil texture wetlands should have a sufficient size in relation to the size of its catchment area in order to provide calm conditions for the settling of particulate matter. In Finland, the recommended size for a constructed wetland for the treatment of agricultural runoff is 1 2% of the catchment area (Koskiaho and Puustinen 2005, Puustinen et al. 2007). Wetlands and ponds falling below the lower limit have shown poor P retention performance, while wetlands exceeding this relative size have been found to retain P over many years (Puustinen et al. 2007, Koskiaho et al. 2009). However, due to the high price of land, the lack of suitable places for construction, and the eligibility limit for agri-environmental subsidy (0.5% wetland-to-catchment area ratio), wetlands that are currently established typically have a smaller area ratio than would be ideal for efficient P retention. Moreover, because the number of agri-environmental wetlands established in Finland so far is not very high (Aakkula et al. 2010), their overall effect on P loading of the surface waters of our country is presumably low Chemical amendments to increase P retention in wetlands Phosphorus retention in wetlands may be accentuated by adding chemicals or a medium that reacts with dissolved P. There are two main options for doing this, namely adding chemicals that dissolve in water and strip P from the water column as a precipitate, or adding in the path of water a solid medium that binds P on its reactive surfaces. The first approach includes metal salts such as ferric or aluminium sulphates and chlorides. Metal salts are widely used in water and wastewater purification and they can be regarded as a proven option that, when combined with wetlands, is applied in a new context. The second approach, solid P sequesters, may involve materials originating from, for example, side flows of industrial or mining operations. The use of retention media is an approach that was presented already in the 1960s (Yee, 1966; Neufeld and Thodos, 1969), and since then has been widely tested in laboratory and shortterm field experiments, but only a few long-term field-scale tests have been reported to date (see Klimeski et al., 2012). MTT REPORT 92 7
8 The use of a solid retention medium has several potential advantages over the use of soluble chemicals. First, after the construction of a structure that holds the solid material the need for maintenance is less than for soluble chemicals that require continuous oversight. Another advantage of a solid medium is that P is retained in the structure and P removed from the aquatic system when the used medium is changed. This may also allow the recovery of the P collected in the medium in a form that can be recycled in fertilizers. Further, depending on the medium, possible hazards associated with overdose are likely to be less than when soluble chemicals are used. There are, however, prerequisites for using solid P retention media. The material should have a high affinity for P, it should be permeable and maintain sufficient hydraulic conductivity in variable flow conditions, and it should be non-toxic for water organisms (preferably only modest effects on, for example, the ph of water, low in soluble heavy metals, etc.). Ideally, the material would also have a good availability and price making the use feasible in selected applications and sites. A number of different types of materials have been tested as potential P retention media. The most interesting are those that contain abundant Ca or Mg in a form that is entirely or partly soluble, and those that contain metal (Al or Fe) hydroxides that are known to have a high affinity for soluble P. There are also materials that contain both metals and soluble Ca or Mg (or both), such as steel slag which typically contains iron in relatively high concentrations, but also soluble Ca oxides as a result of heating the ore and additives (e.g. charcoal) to high temperatures. The total concentrations of the listed elements cannot, however, be used as the sole selection criterion as they should be in a form that is reactive, thus having an affinity for P. For example, iron oxides with a highly ordered crystalline structure are much less reactive than poorly crystalline iron hydroxides, why the latter are a better candidate as a P sequester material. As stated above, most of the testing reported in academic articles originates from studies conducted in laboratory. The large scale studies reported include studies of wastewater in England (Heal et al., 2004; Dobbie et al. 2009) and New Zealand (Shilton et al., 2006). The P retention material in the studies of Heal et al. (2004) and Dobbie et al. (2009) was mine drainage residual, or ochre, which is an iron hydroxide precipitate; whereas steel smelter slag was tested by Shilton et al. (2006). Similar materials have been also tested to treat agricultural runoff in the US (Penn et al., 2007, 2012) and New Zealand (McDowell et al., 2007). Materials that contain only Ca have been studied on larger scales by, for example, Kirkkala et al. (2012). The longest field study is probably that of Shilton et al. (2006) who followed for 11 years a large (>1000 m 3 ) steel works slag filter installed in a wastewater treatment plant. Phosphorus concentration of the feed liquor was at about 8 mg l -1, and the filter lowered it by 75 80%, to about 2 mg l -1, during the first five years of operation. After that P retention started to gradually decrease with time. High initial P removal efficiencies were also reported by Dobbie et al. (2009) and Penn et al. (2007) for mine drainage residuals, and by McDowell et al. (2007) for steel works by-product. Kirkkala et al. (2012) in turn measured 46 62% P removal efficiencies during years for three different lime (CaO/Ca(OH) 2 /CaCO 3 ) filters that were buried in soil and took variable flows of ditch or runoff water. Lime caused the precipitation of soluble P and, as shown by the high ph in outflow of their filters (up to ph value of 12 in one of the filters), the filters had reactive lime present throughout their study period. There are thus examples of solutions that have worked well, at least for some periods. 1.2 Project description and objectives The core idea of the Active Wetlands project was to find out how the efficiency of small wetlands in nutrient retention could be improved. The project was a joint effort of the following Finnish and Estonian partners: - MTT Agrifood Research Finland, Plant Production section (MTT) - Finnish Environment Institute, Research Department/Research Programme for Integrated River Basin Management (SYKE) - Turku University of Applied Sciences (TUAS) - WWF-Finland (WWF) - Estonian Fund for Nature (ELF) - Estonian University of Life Sciences, Institute of Forestry and Rural Engineering, Department of Water Management (EULS) 8 MTT REPORT 92
9 The main objectives of our project were: 1. To generate knowledge and explore the applicability of different active measures to increase the efficiency of small wetlands in P retention (i.e., to develop active wetlands). 2. To test practical designs for constructing active wetlands on a field scale. 3. To raise public awareness of the use of active treatment of agricultural runoff and to discover the attitudes of farmers to such methods. 4. To test the potential of active wetlands in nutrient retention of agricultural runoff at the watershed level through mathematical and economic models. 5. To assess the possibilities of including the active measures in nutrient sequestration to agricultural policy. 6. To develop trans-boundary co-operation of the concept active wetlands by sharing ideas from local/regional/national wetland design, construction and management, and by improving together public awareness of wetlands and their potential in nutrient retention from agricultural runoff. The project s findings are published in two separate reports. This report focuses on constructing and testing new methods that would enhance P retention in watersheds, including basic calculations on the site-specific costs and benefits of the methods tested. We also include in this part aspects of public opinion and farmers views on the use of chemicals for P sequestering from agricultural runoff. As a result, this report focuses on objectives 1 3, whereas objectives 4 and 5 are discussed in a separate report that takes an in-depth look at the modelling work. Objective 6 has been worked on since the beginning of the project and a lot has been learned within the project from the experiences in different areas. The entire project was funded by the European Regional Development Fund, Central Baltic Interreg IVA programme during Permissions and legislation When planning chemical treatments as a part of nutrient mitigation projects, different kind of permissions are needed. For all activities the permission of the land and/or water owners is naturally required. Additional permissions and documentation may vary widely, depending on where the planned activities take place. Here we describe the process of applying for permissions for chemical use at two sites, one in Finland and the other in Estonia. Experiences in Finland In Finland, small treatment units placed in minor ditches need to be notified to the local Centre for Economic Development, Transport and the Environment (ELY Centre). Any constructions or actions in larger streams, or other actions that may be regulated by the Water Act (587/2011) or the Environmental Protection Act (86/2000) require permissions from the Regional State Administrative Agencies (AVI, Aluehallintovirasto). The Finnish study sites built in this project were located in minor ditches and thus gained approval from the ELY Centres of the regions in question. Each application letter stated the following points: - the aim of the activity and its duration - specified sites, marked in maps - landowners and their statements of approval - chemicals to be used (with product data sheets as appendices) - detailed plans on how the constructions are to be done and how they might affect the surrounding land and recipient water - how the activities and their effects are followed during the tests In their response, ELY Centres stated that it is not likely that the described activities would cause any harm to the environment or the surroundings, and hence testing could be conducted once the landowners agree. In addition, responsibility for any possible damage to the surroundings, the neighbourhood, land owners, etc., is governed by the Water Act and falls on the party that conducts the actions. MTT REPORT 92 9
10 In Finland, there are no specific guidelines for the chemical or physical properties of (soluble or solid) materials used for the treatment of runoff waters in small ditches, but their suitability is judged by ELY Centre personnel. Obviously, the application of directly toxic elements is not permitted, but, for example, changes in the ph of water due to the treatment or content and solubility of heavy metals (or other potentially harmful elements) in the materials have no stated guideline values. When applying for the permits we referred to guideline concentrations for soil amendments, which apparently satisfied the ELY Centres. At present, the sites where chemicals or solid P sequesters are used are very few, and it is likely that there will be limits on the chemical properties of these types of materials in the future, especially if small scale testing is a success and interest in the wider use of these methods increases. Experiences in Estonia In Estonia, any treatment of agricultural drainage waters is regulated by the Water Act (RT I 1994, 40, 655) and the Ministry of the Environment Regulation No. 18 entitled Proceedings for issue, amendment and revocation of permits for the special use of water and temporary permit for special use of water, a detailed list of the information necessary for applying for a permit and the format of an application for a permit (RTL 2002, 48, 664). The Water Act specifies the main legal obligations and regulation of activities, whereas a permit for the special use of water is necessary if a water body is dammed, resulting in the alteration of the water table by 0.3 m or more, or chemicals are applied to water. The Environmental Board, operating under the Ministry of the Environment, can issue permits for the special use of water after considering an application. The application should contain the following: - name or business name, registry code, if one exists, and the domicile of the applicant - location of the activities for which the permit for special use of water is applied - a short description of the activities for which the permit is applied (the duration of the activities, chemicals to be used, description of the treatment unit construction) - measures reducing the effect of special use of water on water bodies and recipients, and the terms for application of the measures - damming effects on the surrounding land - permission of the landowner(s) - permission of the municipality. The issuer of the permits for special use of water announces the permit in the official publication Ametlikud Teadaanded within seven days after issuing it. A prerequisite for a successful application is that the quality of the water body in question shall not deteriorate as a result of the actions. The assessment of the status of water bodies is based on Ministry of the Environment Regulation No. 44: Procedures for establishing surface water bodies, list of surface water bodies whose status class is to be determined, status classes for surface water bodies and procedures for determining quality indicator values corresponding to the status classes (RTL 2009, 64, 941). This regulation establishes the quality indicators and the procedures for classifying water bodies. Estonian legislation recognizes five classes of water bodies, depending on the purity of the water, with the designations and guideline concentrations for total nitrogen (N) and phosphorus (P) presented in Table 1. Table 1. Estonian classification of water quality by the guideline concentrations of total nitrogen and phosphorus. High Good Moderate Somewhat Poor Quality indicator poor Ntot, mg l -1 < > > > 8.0 Ptot, mg l -1 < > > > 0.12 The classes High and Good correspond to the status of unpolluted natural water, or a status close to that. Moderate water quality relates to water bodies on which human activity has had a moderate impact. The classes Somewhat poor and Poor include water bodies that are considered to be polluted, or highly polluted, by human activity. 10 MTT REPORT 92
11 2 Material and methods 2.1 Selection of test sites Site surveys in Finland A preliminary search for suitable test sites (selection criteria discussed later under subheading 2.1.3) in Finland was conducted among the wetlands that were known to exist in the south of the country; for example, the WWF has built tens of wetlands in agricultural areas in Finland. During this search 12 wetlands were visited and samples were taken. However, after laboratory analyses of the water samples taken from these sites it became clear that almost none of them had P concentrations high enough that the use of chemical methods would be justified. Following discussions with the project steering group, it was agreed that in order to study the core topic of the project, i.e., to discover the potential of the methods of active P removal, the tests should not be exclusively carried out at sites with an existing wetland or a sedimentation pond, but the methods could be also tested at other sites that had elevated concentrations of dissolved P in ditch water. The following second survey was extended to an additional 23 sites, a number of which were known from the earlier work of the institutions to deliver high-p waters. At the beginning of 2010, TUAS conducted a separate site survey in order to find a suitable ditch and wetland for the pilot studies. The survey was carried out in Turku and its neighbouring municipalities. Potential sites were selected in a map survey and an enquiry was directed to wetlands planners. For the final site selection, water samples were taken from three potential sites. From the information collected, a small agricultural ditch located in Lieto was selected for the pilot studies. 21 E 22 E 23 E 24 E 25 E 26 E Sampled wetlands/ditches Pilot sites 61 N Turku " Su Na Nu 1-10 Oj So 1-3 Ha Ta Ar Su Mu Ri Pa " Hämeenlinna Ho Vi La " Pu 1-5 Lahti St 1-2 Kr Helsinki " 60 N 0 50 Km Figure 1. The locations surveyed in Finland. The final test sites are marked with green markers. The sites are identified on this map using the two first letters of their names (see Figure 2). The pilot tests were finally run in 17 locations in Finland, three of which were associated with a wetland. Of the wetland sites, one (Hovi) did not receive any chemical amendment, whereas P precipitation by soluble metal salt (ferric sulphate) was tested on one site (Nautela) and a solid P requestor material MTT REPORT 92 11
12 (Sachtofer PR Ca-Fe oxide granules) at the other site (Ojainen). The rest of the tests were run in ditches that drained variable types of watersheds. The surveyed locations and the selected test sites are shown in Figure 1, and the P concentrations at all sites in Figure (19.3) (4.0) (0.9) (1.4) Dissolved P, mg l (32.4) (5.6) (4.7) Total P, mg l * Pauninoja * Suvikuva * Riuskanoja * Mustiala Aronkulma Kallio * Ojainen Rehtijärvi * Suominen * Nautela Strandby1 * Strandby2 * Krapunoja * Hajala Lahdenpohja Vironjoki Puraila1 Puraila2 Puraila3 Puraila4 * Puraila5 Nuutajärvi1 Nuutajärvi2 Nuutajärvi3 Nuutajärvi4 Nuutajärvi5 Nuutajärvi6 Nuutajärvi7 Nuutajärvi8 Nuutajärvi9 Nuutajärvi10 Somero1 Somero2 Somero3 * Hovi Figure 2. Concentrations of dissolved P (upper graph) and total P (lower graph) in water samples collected during site surveys in Finland. The numbers in parentheses show the concentrations that exceed the y-axis scales. Wetland sites are marked with asterisks Site surveys in Estonia From May 2010 to November 2011 EULS and ELF made an extensive, country-wide survey of possible test sites in Estonia (Figure 3). For the survey, data from the State Environmental Monitoring Programme were searched for elevated P concentrations in river water across the priority counties of the INTERREG programme (i.e., those bordering the Baltic Sea). In the second stage, satellite photos and map databases of the catchments of selected rivers were searched for farmland and drainage ditches, so that potential pilot sites could be located. After that, the locations were visited, and, if the site seemed appropriate, a water sample was taken for nutrient analyses. During this survey 79 water samples were collected to map the quality of agricultural drainage waters (Figure 4 and 5). According to the results, the water quality parameters of 10 ditches indicated Poor quality associated with severe pollution by human activities. The sites were located near large farms, in areas with intensive agricultural activity, or downstream of less well functioning wastewater treatment facilities. Alongside water quality, the final site selection was made by taking into account land ownership, the willingness of land owners to co-operate, and accessibility to the site. During this process some sites had to be discarded; for example, a good candidate site at Arkna in Northern Estonia was investigated further. Several additional water samples that were taken from the Arkna ditch indicated poor water quality, with total phosphorus and total nitrogen concentrations of mg l -1 and mg l -1, respectively. 12 MTT REPORT 92
13 However, the site was far from any road and during the wet periods (when sampling would be most intensive) the site became practically inaccessible. Finally, a field area in Rahinge, Tartu, proved to be an ideal candidate, with high dissolved P concentrations and easy access, ensuring that the site could be visited daily. Figure 3. The locations surveyed in Estonia Selection criteria for the test sites In the evaluation of potential test sites we initially applied the following criteria: - a wetland exists or is easily constructed in a ditch that drains areas with agricultural activities, preferably animal farms within the proximity of the site; - phosphate concentration in water exceeds the normal concentration level for agricultural runoff; phosphate concentrations were considered normal when at about the 100 µg l -1 level or lower; - the optimal size of the catchment would be 30 ha or less; the larger the size of the catchment, the higher the peak flow volume and thus bigger units should be built for testing; - sampling of water before and after the test site should be possible, meaning that there would be some slope in the ditch; - on sites with a higher flow, a Ferix doser was considered a more appropriate alternative than solid P retention buffers, because of the lower risk for ponding the site over field drain outlets; - for solid P retention materials, a buffer size of about 3 m 3 was considered optimal, as it could be fitted to relatively small ditches. After visiting a number of existing wetland sites in both participating countries, it became impossible to find wetlands that met all of these criteria. At only a couple of the existing wetlands did the phosphate concentration exceed the above criterion. The low concentrations were either because most of the wetlands did not receive high-p waters at all, or, if there were some smaller areas in the catchment that had high P loading potential, water from these was diluted by pure water before entering the wetlands. MTT REPORT 92 13
14 0,6 0,5 Total P, mg l -1 0,4 0,3 0,2 0,1 Total P, mg l -1 0,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 Tännassilma Tännassilma Tännassilma Lota ditch Ühenduse- Sääsküla stream Särgjärve Särgjärve Rõhu Rahinge ditch Ilmatsalu river Rahinge ditch Kandi stream Rahinge ditch Koosa stream Lubja stream Kiivitasoo ditch Müüri stream Kastolatsi stream Restu ditch Kirikusoo stream Tiidu village ditch Keeni stream Pringi stream Lota stream Harjava ditch Rebase ditch Juuliku ditch Jälgimäe ditch Haljala stream Näpi stream Sõmeru river Vända ditch Vända ditch Valingu ditch Tuula ditch Tuula-2-II Silla I/Jõe II Humala stream Vaeküla stream Arkna ditch Kärsa - Saare stream Kärsa stream Tammistu ditch Ätte ditch Kardla ditch Ditch behind the barn in Käina Vaemla bridge 4th Käina ditch Tobias ditch Porijõgi river Porijõgi river Porijõgi river Tatra river Main ditch flowing into Peeda river Porijõgi river Tatra river Liudsepa stream Tatra river Unipiha drainage canal Visnapuu ditch Pühi ditch Pühi ditch Peeda river Peeda river Luhasoo stream Lubja stream Idusoo stream Peeda river Porijõgi. Kaatsi Sipe stream Porijõgi river Sipe stream Sipe stream Vända main ditch Tatra river Figure. 4. The concentrations of total phosphorus from sampled sites in Estonia. The dotted line indicates the limit value for "Poor" water quality. 14 MTT REPORT 92
15 Total N, mg l Tännassilma stream I Tännassilma stream II Tännassilma stream III Lota ditch Ühenduse-Liivaaru ditch Sääsküla stream Särgjärve Särgjärve Rõhu Rahinge ditch Ilmatsalu river Rahinge ditch Kandi stream Rahinge ditch Koosa stream Lubja stream Kiivitasoo ditch Müüri stream Kastolatsi stream Restu ditch Kirikusoo stream Tiidu village ditch Keeni stream Pringi stream Lota stream Harjava ditch Rebase ditch Juuliku ditch Jälgimäe ditch Haljala stream Näpi stream Sõmeru river Vända ditch outlet Vända ditch inlet to lake Valingu ditch Tuula ditch Tuula-2-II Silla I/Jõe II Total N, mg l Humala stream Vaeküla stream Arkna ditch Kärsa - Saare stream Kärsa stream Tammistu ditch Ätte ditch Kardla ditch Ditch behind the barn Vaemla bridge 4th Käina ditch Tobias ditch Porijõgi river Porijõgi river Porijõgi river Tatra river Main ditch flowing Peeda river Porijõgi river Tatra river Liudsepa stream Tatra river Unipiha drainage canal Visnapuu ditch Pühi ditch Pühi ditch Peeda river Peeda river Luhasoo stream Lubja stream Idusoo stream Peeda river Porijõgi. Kaatsi Sipe stream Porijõgi river Sipe stream Sipe stream Vända main ditch Tatra river Figure 5. The concentrations of total nitrogen from sampled sites in Estonia. The dotted line indicates the limit value for "Poor" water quality. MTT REPORT 92 15
16 2.2 Tested chemicals Ferric sulphate and its dosing For stripping P with soluble metal salt we tested ferric sulphate, Fe 2 (SO 4 ) 3 with the trade name Ferix-3 (Kemira Kemwater, Helsinki, Finland). Ferix-3 is used in municipal waste water treatment plants and in tap water production to precipitate solids, organic matter and dissolved P. It has an iron content of about 20%, with the iron entirely in an oxidation state +III. The chemical is soluble in water so that (weight-%) solutions are stable to use. Ferric sulphate falls into the chemical hazard class irritating, but with a ph of water solutions less than 2. Consequently, care should be taken upon handling the chemical. Ferix-3 comes in granules with a typical mean diameter of 2 mm (96% between mm) and it has a volume weight of 1.2 kg l -1. For dosing of Ferix-3, we used a doser previously developed at MMT by Aaro Närvänen (see Närvänen and Jansson, 2007; Närvänen et al., 2008). A schematic picture of the doser and two units in operation are shown in Figure 6. The unit consists of a chemical storage ( litre sand box) that has one or two 200 mm polyethene pipes attached through the bottom, and a cone-shaped polyester netting(s) attached to the lower end of the hanging polyethene pipe. Ferix-3 is fed from the storage to the polyethene pipe by gravity and down to the netting cone where water dissolves the chemical. When the water level in the upstream part of the v-notch weir rises, more of the netting cone is submerged (more surface area of the chemical containing cone is exposed to water), and more Ferix-3 dissolves. As a result, an increase in water flow leads to a dissolution of higher amounts of the chemical in the water. It is possible to adjust the dosing of the chemical by changing the angle of the v-notch weir; in this work the v-notch weirs were in some cases at 90, but mostly 120 angles. The 120 angle is usually sufficient when the ratio of administered Ferix-3 to ditch water is one kilogram of Ferix-3 to about 50 m 3 of water (1:50k). This has been found in earlier tests to cause precipitation of most of the dissolved P, but without precipitation of much of the suspended solids. The precipitation of solids would have resulted in the production of large volumes of sludge that would have certainly caused aesthetic issues. With the 1:50k dosing the amount of sludge was moderate. Some units were equipped with 90 v-notch weirs, but in those cases the ditches were a few meters distant from joining a larger channel, and a higher amount of Ferix-3 was dosed to supply also the larger channel with some of the chemical. Sand box Ferix-3 Poyethene pipe Poyester netting cone Water flow V-notch weir Figure 6. Upper graph: schematic figure of the Närvänen-type Ferix doser. The photographs show a smaller doser unit (left-hand) that is sized for relatively small ditches, and (right-hand) a larger unit that is equipped with two doser socks and a 600-litre storage compartment to ensure a high enough feed during peak flow. Photographs by Aaro Närvänen. 16 MTT REPORT 92
17 For the selection of the proper size of Ferix doser units for the pilot sites, an assessment of the amount of ferric sulphate needed to be fed for each ditch was based on an empirical equation (according to earlier laboratory work at MTT): The amount of chemical needed (in kg yr -1 ) = C P b m P [Eq. 1] In Eq. 1., C P is the typical concentration of dissolved P in water (mg l -1 ), b is calculated as: 100/Fe content of the chemical (in %; for Ferix-3 this ratio is 100/20 = 5), and m P is the annual load of dissolved P (in kilograms) that is to be treated. The cost of Ferix-3 was found to be highly variable, largely depending on the quantity bought at one time. The lowest cost was 0.35 eur kg -1 (excl. VAT), purchased for the Nuutajärvi tests, and the highest 0.55 eur kg -1 (excl. VAT) for the Nautela tests; the cost of Ferix-3 purchased for the Nautela tests increased (from 0.46 eur) by 18.5% over the two years of testing Tests with solid P retention media Two types of solid retention media were tested in this project. The material tested in both participating countries was Sachtofer PR, which is a granular product manufactured by Sachtleben Pigments plant in Pori, Western Finland. The other material tested, only in Estonia, was waste ash obtained from an Estonian electrical power plant fuelled with crushed oil shale. Solid P sequesters are used as permeable barriers through which water flow is directed. Because the reactions linked with P retention are either sorption (attachment to, for example, Fe and Al oxides) to the surface of material, or precipitation of sparsely soluble phosphate species (e.g., Ca-P precipitates), water must come into good, long enough contact with the P retention material. For precipitation reactions the material must also be able to supply enough soluble cations (e.g., Ca 2+ ) so that the solubility constant of a given precipitate is exceeded. For efficient precipitation, the ph of the solution has to be on the basic side of the ph scale. For a more thorough discussion on P retention mechanisms and materials, see, for example, Klimeski et al. (2012). Sachtofer PR granules Sachtofer PR is a granular material that contains Ca and Fe, obtained as a co-product of titanium dioxide pigment and associated ferrous sulphate production at the plant of Sachtleben Pigments Oy in Pori, Western Finland. The material is made by mixing acidic ferrous sulphate (FeSO 4 ) with calcium oxide (CaO) and water in a granulator. The end product s chemical composition is mostly gypsum (CaSO 4 2 H 2 O) with about 10% Fe content (likely as a mixture of Fe hydroxides and oxides, FeOOH, Fe 2 O 3 ). When stirred into water the ph rises to about 9 11, which indicates presence of Ca(OH) 2. The volume weight of the granules is about 1.5 kg dm -3. The granule size of the product varies, but usually 90% of the mass consists of greater than 1 mm particles. The manufacturer s estimate of the price at the plant-gate is EUR per tonne. Due to the lack of official limits for harmful elements in materials that are used for the purpose of P retention in wetlands or ditches, the concentrations of metal elements in Sachtofer PR were compared to those for which there are guideline concentrations in the statute (Statute No. 9/09 of the Ministry of Agriculture and Forestry, Finland) associated with the Fertilizer Product Act (539/2006). The contents of potentially harmful elements were found to be less than the guideline concentrations for soil amendment materials, or, with the exception for total chromium (Cr), also below the permissible concentrations for fertilizer products. As of Cr, the concentration of the toxic, water-soluble form, Cr(VI), is below the guideline limit. In this work we analysed Cr and Ni concentrations in water samples (during the unfrozen period at about one-month intervals) from the start of the field test done in Jokioinen, Finland, (launched in 2010) to the end of 2012, but did not find that the Sachtofer PR granule buffer would have elevated the Cr or Ni concentrations in water; the Cr concentrations remained below 2 µg l -1 and the Ni concentrations below 6 µg l -1, i.e., below or at the detection limit of the ICP analyser used. According to an earlier laboratory study (Uusitalo et al., 2012), the granules have a P retention capacity that is an order of magnitude higher than what Finnish soils typically have, and they can be regarded as efficient P sequesters. According to the earlier study, more than 50% of the retention of dissolved P can be obtained in 30 minutes contact or longer with water, which means that a P barrier made of Sachtofer PR granules could be a suitable mitigation option for relatively small drainage areas. Because of the MTT REPORT 92 17
18 relatively high cost (EUR per Mg -1 ) Uusitalo et al. (2012) stated that cost-efficient use of this material will be restricted to sites with a high P concentration in the water. In the current project, the Sachtofer PR granules were tested at one site in Finland and at one site in Estonia. The Estonian University of Life Sciences also conducted further studies on the granules on smaller scales. Oil shale ash Oil shale ash is a Ca-rich residue derived from burning in electric power plants low-caloric value solid fuel oil shale (kukersite) in Estonia. The utilization of oil shale leaves after combustion 45 48% of the oil shale dry mass (Bauert and Kattai, 1997), and totally about 6 8 million tons of waste ash is produced annually at Estonian power plants. The ash removal at electric power plants is managed by hydraulic transportation of ash-water slurry mixed at a ratio of 1:20. The piled ash plateaus near power plants cover an area of about 20 km 2 and contain about 300 million tons of hydrated ash (Figure 7). Figure 7. Ash platheus in Estonia. Photographs by Egle Saaremäe. Estonian oil shale is highly calcareous, with a calcite/dolomite content of 40 60%, and the ash remaining after combustion is due to thermal decomposition of carbonate minerals and subsequent reactions with sulfur-containing flue gases rich in highly reactive free lime (CaO) and anhydrite (CaSO 4 ). In addition, the ash contains an amorphous aluminum-silicate glass like phase and a variety of Ca(Mg)-silicate minerals from decomposition and reactions between clay minerals, K-feldspar, quartz, and CaO. Lime and anhydrite begin to react with water in the ash removal system, and the hydration processes continue in the piles, forming a variety of secondary Ca minerals such as ettringite, Ca-aluminates, and calcite (Liira et al., 2009a). Kaasik et al. (2008) have shown that hydrated oil shale ash is composed of several Ca-phases including calcite and vaterite as Ca-carbonate phases (CaCO 3 and γ-caco 3, respectively), ettringite [Ca 6 Al 2 (SO 4 ) 3 (OH) 12 26H 2 O], hydrocalumite [Ca 2 Al(OH) 7 6H 2 O], portlandite [Ca(OH) 2 ], C2S belite [β-ca 2 SiO 4 ], merwinite [Ca 3 Mg(SiO 4 ) 2 ], melilite [(Ca,Na) 2 (Al,Mg,Fe)(Si,Al) 2 O 7 ] and wollastonite [CaO SiO 2 ]. About 10 20% (maximum 40%) of the ash consists of amorphous glass-like aggregates of (alumino-) silicate composition (Mõtlep et al., 2010). 18 MTT REPORT 92
19 Estonian oil shale is characterized by generally low micro- and heavy element concentrations. Similar to the shale, the content of trace/heavy elements in oil shale ash is low and does not exceed the average concentration in the Earth s crust, except for Mo and Pb (Table 2, after Ots, 2006 and Kaasik et al., 2008). Table 2. Average concentrations of selected trace elements in hydrated plateau sediments and the Earth s crust (after Ots, 2006 and Kaasik et al., 2008). N/A = data not available. Element Ash-plateau sediment Earth's crust mg kg -1 Ni Mo Cu Pb Cd < As Sc 6.0 N/A Zn 50.3 N/A Veskimäe et al. (1997), Vohla et al. (2005), Kaasik et al. (2008), Liira et al. (2009b) and Kõiv et al. (2010) have shown in laboratory experiments the effectiveness of Ca-rich hydrated oil shale ash as a possible material for P removal in constructed wetland systems. In laboratory batch studies, P removal by fly ash and hydrated ash may be virtually complete, with maximum binding capacity as high as 65 mg P g 1 (Vohla et al., 2005; Kaasik et al., 2008). Phosphorus retention by this Ca-rich material occurs through adsorption and precipitation into a solid phase. The remarkably high P-binding capacity of the oil shale ash is influenced by the complex physical-chemical properties of the material, especially its high content of different Ca- and Al-compounds, porosity, and high ph. However, there are still no long-term field studies to confirm the applicability of oil shale ash for P removal in practical applications. 2.3 Sampling and methods of water analyses Samplings during the site surveys were done so that at least one sample was taken from each site to obtain an idea of the chemical water quality. In the Finnish survey on wetlands, two samples were taken from each site: one from the inlet and another from the outlet of the wetlands. When the surveys were extended to embrace ditch waters, one sample was taken from each site. Water sampling during the pilot tests was done mostly manually and always comprising a sample pair that was taken from the inlet and outlet of the site. For phosphorus analyses in the laboratory, water samples were split into two, with one portion passed through a membrane filter and the other portion stored as unfiltered. Filtering was done using 0.2 µm pore size membranes, with the exception of the samples that were obtained from the Paimionjoki sites, which were analysed in a commercial lab that used 0.4 µm pore size membranes. The filtered subsamples were analysed for dissolved P, either without digestion or for the Paimionjoki area and Nautela samples after digestion with peroxodisulphate in an autoclave. The digestion step would liberate any P attached to colloidal mineral and organic matter that has passed through the filter membrane used, and the results of dissolved P therefore describe slightly different P pools for the samples that were put through different pre-treatments in the laboratories. However, if the methods applied for retaining P from the runoff water are good at doing their job, the results would nevertheless point in the same direction. The unfiltered subsamples were analysed for total P (and N) concentrations after digestion in an autoclave. Phosphorus analyses were conducted in all laboratories with flow-injection analysers, using modifications of the molybdate blue method of Murphy and Riley (1962). Water ph was measured in the laboratories using electrodes, and (in Nautela) monitored with automatic sensors (YSI Inc., Yellow Springs, Ohio, USA). MTT REPORT 92 19
20 Heavy metal Cr and Ni concentrations were measured from a set of filtered (0.2 µm) influent and effluent samples at the Ojainen site where Sachtofer PR granules were used. This was done to check earlier laboratory findings that these heavy metals do not leak from the material. Measurement was done using an inductively coupled plasma atomic emission spectrometer (ICP AES) at MTT, Jokioinen. Other laboratory analyses were also conducted on water samples, but because of the focus on phosphorus in this report, they will be reported in scientific articles that are currently under preparation. 2.4 Test set-ups at different sites Hovi wetland without chemical amendments Hovi wetland (N , E ) was constructed by MTT and SYKE in 1998 for research and demonstration purposes. The characteristics of the Hovi wetland are presented in Table 3. Table 3. Characteristics of the Hovi wetland Wetland area Catchment area Wetland-tocatchment ratio Mean slope Land use Soil type ha % 100% field Heavy clay (row crops) A schematic map of the Hovi wetland is presented in Figure 8. The most important features of the wetland are (i) distinct deep and shallow areas, (ii) the spits of land that create a tortuous, as-long-aspossible flow path and (iii) dense, uniform vegetation distributing the flow evenly through the shallow zone. All these features create diverse environments for different water purifying processes. Measured water concentrations and runoff as reported by Koskiaho et al. (2009) are presented in Table 4. Table 4. Measured flow-weighted suspended solids and nutrient concentrations in inflow to the Hovi wetland, and runoff from the catchment area, during two earlier monitoring periods. Suspended solids Total P Dissolved P NO 3 -N Runoff from the Hovi catchment mg l -1 mm Figure 8. A schematic map of the Hovi wetland. 20 MTT REPORT 92
21 2.4.2 Nautela tests with ferric sulphate The Nautela site was located in Lieto near the city of Turku, SW Finland. This site was constructed and monitored by TUAS, and equipped with sensors that continuously monitored water flow, the ph and turbidity of the water in two spots in a stream, before and after a ferric sulphate doser. The pilot site is a small ditch surrounded by agricultural fields. There are two constructed sedimentation ponds in a chain, created by bottom dams, about 100 meters apart from each other (see Figure 9). The catchment area of the ditch is about 60 hectares and the share of fields in the catchment is 63%. The main soil type is clay and the fields have a typical slope of less than 3%. The fields were under cereal production during the test period. A ferric sulphate doser equipped with a 350-liter chemical storage and a 120º-angle v-notch weir were installed at the site in the autumn 2010 upstream from the lower pond. A pressure sensor and water level sensor was installed in the vicinity of the weir to enable discharge calculations. Online measurement systems were installed for influent and effluent water quality monitoring (Figure 9), and manual sampling for additional water quality parameters was conducted at these same spots. Due to the ditch freezing over during the winter, the monitoring was by necessity periodic. As the first test period in 2010 was very short, we present the results from the 2011 and 2012 test periods only. These cover the ice-free season from spring floods to the onset of frost in winter. Figure 9. Location of the ferric sulphate doser (marked with red flag) and water quality monitoring spots (marked with blue points). 1 Altogether 58 paired water samples were taken manually from April 2011 to October 2012 for the analysis of dissolved P; two evidently corrupted sample pairs were ignored in the data analysis. Manual sampling was generally done once every one to two weeks, but the flow in the ditch was taken into consideration so that sampling concentrated on high-flow regimes. Continuous water quality monitoring was carried out by online systems every 30 minutes using a YSI 6920 series multiparameter sonde and a S::can nitro::lyser for ph, electrical conductivity, turbidity, oxygen and nitrate concentrations, and water temperature. The water level was continuously monitored by a Keller DCX-22 pressure sensor. The multiparameter sonds were regularly calibrated, and the measured water level was confirmed by comparing with manual water level checks. 1 Orthophoto aerial photograph (3/2013) obtained from the National Land Survey of Finland, Topographic database 06/2012. Licence: MTT REPORT 92 21
22 2.4.3 Lake Nuutajärvi area tests with ferric sulphate In spring 2012 P precipitation by ferric sulphate was tested in 10 ditches draining into Lake Nuutajärvi in Urjala. Lake Nuutajärvi has a history of algal blooms in several summers during the last decade, and the input of dissolved P per area unit of Lake Nuutajärvi is substantial, about tenfold as compared to the next lake (Lake Rutajärvi) in the lake chain. The P sources were earlier studied by MTT (Närvänen et al., 2003) and these data provided us with background data for the initial selection of appropriate sites for testing. The site survey and selection of ditches was done during 6 22 September 2011 in co-operation with the lake protection associations of lakes Nuutajärvi, Rutajärvi and Kortejärvi. The survey included 17 ditches, 10 of which were found suitable for the installation of ferric sulphate dosers. The selected ditches had variable catchment sizes and nutrient sources, some areas were associated with animal husbandry and some with fields only. Four of the sites were small ditches that drained areas of five hectares or less, but also three ditches draining at least 50-hectare areas were included (see Table 5). The site characteristics of all the selected ditches are shown in Table 5 and the location of the doser sites is in Figure 10. All of the ditches selected were located along the main channels that enter the lake. Agreements on the tests with the land and water owners were negotiated by the lake protection associations. All sites were planned and the dosers prefabricated by MTT at the end of The costs of the dosers plus chemicals to be used during spring 2012 were covered by funding from the Pirkanmaa Centre for Economic Development, Transport and the Environment (ELY Centre). The installation of the dosers was carried out by the lake associations under MTT s guidance. Table 5. Characteristic of the selected sites in the lake Nuutajärvi area. Site Catchment area, ha Source of the loading Estimated chemical need/ recommended dosing period 1 < 5ha fields + forest Cowshed, excercise yards 200 kg/spring 2 50 ha fields + forest Cowshed, excercise yards >1000kg/spring 3 appr. 1 ha Cowshed and surroundings 300 kg/whole year 4 < 10 ha Pasture and cowshed area 600 kg/whole year 5 < 5 ha Cowshed, excercise yards 400 kg/whole year 6 appr. 50 ha Fields 1000 kg/spring 7 20 ha Fields 500 kg/spring 8 appr. 5 ha Horse stable area 300 kg/spring 9 > 100 ha Fields and forest (equal shares) 1000 kg/spring ha Horse stable area 100 kg/whole year The test periods were agreed for spring 2012 and spring Concentrating the tests on springtime was motivated by the fact that most of the dissolved P entering the lake is carried by the spring flood. Also, due to the residence time of about seven months in Nuutajärvi, the spring flow has a substantial impact on the summertime water quality of the lake. Hence, by stripping bioavailable P during the spring flow it would be possible to moderate algal growth in the lake with modest efforts. There were three sizes for the dosers built, depending on the expected water flow and P load. The ditch draining from the smallest horse stable area (site 10) was equipped with 150-litre storage box, six dosers (sites 1, 3, 4, 5, 7 and 8) with 350-litre storage capacity, whereas the ditches with the largest catchments or expected P load (sites 2, 6 and 9) were equipped with boxes with a 600-litre storage capacity. Sites 2 and 8 were equipped with double doser socks, where one doser sock operated continuously during all flow conditions and the additional dosing sock operated under a high flow regime to ensure a high enough chemical feed to the peak flow. 22 MTT REPORT 92
23 Nuutajärvi Figure 10. Location of the ditches that were selected for the Ferix dosing tests in the lake Nuutajärvi area. On 3 March 2012 the dosers were ready for use in the selected locations and dosing was started at the beginning of snowmelt on 22 March. Chemicals were distributed and the chemical storage of the dosers was re-filled by volunteers from the lake protection associations. Water sampling was carried out by the Active Wetlands project personnel. At the same time, the Pirkanmaa ELY Centre ran an intensified sampling of water quality of Lake Nuutajärvi, accompanied by additional summertime Secchi depth measurements by the lake protection association River Paimiojoki area and Tammela tests with ferric sulphate The River Paimionjoki has a drainage basin of about 1000 km 2 in SW Finland and it delivers a substantial nutrient load, 60 Mg yr -1 of total P and 530 Mg yr -1 of total N, to the Archipelago Sea. There are a number of animal farms in the area, and agriculture is estimated to contribute by 80% to the P load and by 68% to the N load that discharges to the Baltic Sea via the River Paimionjoki. The Association of River Paimionjoki has been working since 2010 in order to decrease the nutrient load in the river, and together with MTT and WWF conducted a site survey for the selection test sites in this area. Three sites in the community of Somero were found suitable for the installation of ferric sulphate dose (Table 6). Site P1 was installed below a small sedimentation pond, whilst the two other sites were a ditch draining from a field area where pig slurry is applied in most years (P2) and a ditch that passes a piggery/cowshed yard. There was no opportunity to construct wetlands on any of these sites. The P1 site drained directly to the River Paimionjoki and the two other ditches drained to the River Jaatilanjoki, which is a sub-basin of the River Paimionjoki drainage area. The site characteristics of all the selected ditches are shown in Table 6 and the location of the sites in Figure 11. There were two sizes of dosers built, depending on the expected water flow. The ditch draining from the sites P2 and P3 were equipped with 350-litre storage boxes, whereas the ditch with the larger catchment (P1) was equipped with a box with a 600-litre storage capacity. All of these devices were equipped with one doser sock. Installation on the sites was carried out in September and October 2012, and the tests were launched in October. The doser P3 was in use from 8 October and the two others (P1 and P2) from 15 October until 5 November The re-fill of the chemical storage and sampling of water was carried out by personnel from the Association of River Paimionjoki. Frost at the beginning of November ended the tests so that the total time for testing was only about one month. MTT REPORT 92 23
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text:
Waffle Pump - 1568 - Navy. Waffle Pump is an exciting new brand that is now being stocked by Unique Soles. The 1567 style is the basic Children's style, in Navy elasticated fabric which is interwoven all over, giving a breathable and comfortable fit. The white super light weight sole makes them ideal for exploring on warm summer days and finished off with a red soft faux leather heel cup with their name and logo.
- Price: £29.99 - Out of Stock
- Brand: Waffle Pump
- Color: Navy
- Model: Waffle Pump - 1568 - Navy
- Product ID: 1568-nvy

subset: commoncrawl


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Games in Windows XP such as Solitaire, FreeCell, and Minesweeper are nice distractions — nothing blows off steam like a good round of 3D Pinball for Windows, especially in full screen mode with the volume cranked all the way up!
3D Pinball for Windows has nine rank levels, ranging from Cadet to Fleet Admiral. Complete each mission and advance to the next rank, but you go back to Cadet at the beginning of each game. Here are a few secret codes to get more enjoyment out of 3D Pinball. Note that the 3D Pinball window must be active for these codes to work.
- Regain your old rank from a previous game by starting a new game and immediately typing rmax. Each time you type this secret command, you'll advance one rank level.
- Get an extra ball while the Awaiting Deployment message displays by typing 1max.
- Activate the Gravity Well by starting a new game and immediately typing gmax.
- Get an unlimited number of balls and essentially play for as long as you like by starting a new game and immediately typing bmax. Each time you lose a ball, a new one will appear. (While playing with an unlimited number of balls, none of the other tricks will work.)
- Control the ball with your mouse by starting a new game and immediately typing hidden test. When you do, you can click the ball with your left mouse button and essentially drag it anywhere you want and rack up an unbelievable number of points.
Keep in mind that there isn't a text box into which you enter these secret codes — you simply type them.
Note: This tip applies to both Windows XP Home and Windows XP Professional.
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Check out the Windows XP archive, and get more hands-on Windows XP tips.
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Full Bio
Greg Shultz is a freelance Technical Writer. Previously, he has worked as Documentation Specialist in the software industry, a Technical Support Specialist in educational industry, and a Technical Journalist in the computer publishing industry.


text:
{ENK} Vegas Recap
Aug 22, 2014
20 comments:
my LNA pieces are STAPLES. in fact, i'm wearing my easy, comfy goes with anything navy LNA skirt right now.ReplyDelete
I'm digging the backwards cap with the all black outfit. Ant that's so fun you co-hosted a party with Whitney. :] // itsCarmen.com ☼ReplyDelete
This sounds so cool!ReplyDelete
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Sounds like you really enjoyed yourself! Love the pictures xReplyDelete
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Awesome! Love these pics xReplyDelete
Looks like a cool time! Love LNA.ReplyDelete
looks amazing! whitney port is awesome!!ReplyDelete
I just checked out your post featuring the leather jacket from Whitney's collection, I adore it and look forward to seeing more of her stuffReplyDelete
Omg you got to meet Whitney! Super jealous xReplyDelete
OMG I LOVE ITReplyDelete
Fun! and I can't believe you got fresh coconut water :)ReplyDelete
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WHITNEY. i love her!ReplyDelete
i adore whitney port! looks like this was such a fun event!ReplyDelete
Looks like you had a great time and love your pictures as usual! xxReplyDelete
Really there are variation of attraction of these picture's.I love it.ReplyDelete
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nice post. i wait the updateReplyDelete
You look amazing. I love that hat :)ReplyDelete
Really I appreciate you……I just check out the blog Today.Nice designs cloths...I wish it look to seeing more Designer wholesale clothing apparel......ReplyDelete
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