Phosphorus distribution, forms and dynamics of riparian zone peat wetland in Kristianstad district, Southern Sweden Fosfordistribution, former och dynamik i torvvåtmark i Kristiandstadsområdet, södra Sverige Master of Science Thesis (Examensarbete) 140, 2004 Ann Fristedt Supervisors: Professor Erasmus Otabbong Department of Soil Sciences Swedish University of Agricultural Sciences (SLU) P.O. Box 7014, SE 750 07 UPPSALA Sweden Dr. Elve Lode Department of Forest Soils (SLU) P.O. Box 7001 SE 750 07 UPPSALA, Sweden Abstract Fristedt, A. 2004. Phosphorus distribution forms and dynamics of riparian zone peat wetland in Kristianstad district, Southern Sweden. MSc Thesis. The objectives of this study were to determine total phosphorus (P) status and distribution in the soil profile and to evaluate the impact of season on P dynamics. The soil was taken from a riparian zone peat wetland in Kristianstad district, Southern Sweden. The wetland is adjacent to the nutrient rich-stream Vinneå, which inundates the site regularly, especially during winter and spring. The soil samples were taken at 20 cm intervals down to a depth of 1 m. Three replicates were taken in each layer. Samples were taken on five occasions (September, October, November 2000 and April, June 2001). The samples were air-dried, crushed and sieved (≤ 2mm). A sequential fractionation was then conducted in four stages using: anion exchanger (resin) → 0.5 M NaHCO3 → 0.1 M NaOH → 1 M HCl. Furthermore, Total-P was determined by fusion and P extracted by NaHCO3 and NaOH was broken into organic P (OP) and inorganic P (IP). By subtracting P extracted by resin, NaHCO3, NaOH and HCl from Total-P, a value for Residual-P was obtained. The Total-P content varied between 1434 and 4319 mg/kg in the profile and most P was organically bound (66-79% of Total-P). The highest amounts of P (2553-4319 mg/kg) were found in the upper 40 cm of the profile. The Total-P content decreased during the winter. The results show that P extracted by NaOH and NaHCO3 and Residual-P made up about 95-97% of Total-P. Most transformations seemed to occur in spring and early summer. pH varied between 3.9 and 5.3. Pearson’s linear correlation coefficient suggested significant redistribution among NaHCO3-P into NaOH-P and Residual-P or vice versa. It also suggested significant redistribution among HCl-P into Residual-P and NaOH-P or vice versa. In this study, only soil samples were examined but it would be interesting to investigate inflows and outflows of P via the inundating river or percolating groundwater. The uptake in plants and the input via the large flocks of geese that spend the winter in southern Sweden also require investigation. Key words: phosphorus forms, fractionation, riparian wetland, peat, season, Southern Sweden 2 Sammanfattning (Swedish summary) Fosfor (P) är en begränsande faktor för primärproduktionen, speciellt i vattensystem. En överbelastnig av näringsämnen (eutrfiering) i tex sjöar kan orsaka obalans i ekosystemet med ökad primärproduktion. I slutändan kan detta orsaka snabbare igenväxning och syrebrist på botten. Eutrofiering kan leda till förändring av artsamhällets sammansättning där blågrönalger tar över. Dessa alger är ofta toxinbildande och många arter har dessutom den konkurrensfördelen att kunna fixera luftkväve (N2). Sjöar övergår naturligt till ett eutrofierat stadie i dess succession. Mänskliga aktiviteter påskyndar denna succession genom diverse utsläpp, så kallad kulturell eutrofiering. En del av den överflödiga näringen har sitt ursprung i jordbrukslandskapet, där P lakas ut genom marken eller via partiklar och ytavrinning. Få P undersökningar har dock gjorts på mark som inte brukas och som är vegetationstäckta året om. Denna studie gick ut på att undersöka jorden på en obrukad äng med avseende på P. Studien utfördes inom EU-projektet PROWATER på en provplats i Kristianstad området i södra Sverige. Platsen som valdes är en slåtteräng där jorden består av torv. Ängen översvämmas årligen under vinter och vår av den intill liggande näringsrika Vinneå. Hypotesen för studien var: Markfosfor omvandlas och dess former omfördelas i varandra beroende på säsong. Hypotesen prövades genom att 1) Bestämma totalfosfor status och distribution i marksprofilen; 2) Dela upp totalfosfor i olika fraktioner; 3) Utvärdera säsongernas påverkan på fosfordynamik. Jordprover togs på olika djup med 20 cm intervall ner till ett djup på 1 m. Tre replikat togs vid varje djup och prover togs vid fem tillfällen (September, Oktober, November 2000 och April, Juni 2001). Proverna lufttorkades, maldes och silades (≤2 mm). En stegvis fraktionering med avseende på P gjordes: anjon bytare (resin) → 0,5 M NaHCO3 → 0,1 M NaOH → 1 M HCl. Total-P bestämdes genom föraskning och uppslutning. Fraktionerna utlösta av NaHCO3 och NaOH delades dessutom upp i oorganiskt P (IP) och organiskt P (OP). P som inte gick att lösa ut i fraktioneringen, kallad Residual-P, erhölls genom att subtrahera P extraherat med resin, NaHCO3, NaOH och HCl från Total-P. Total-P varierade mellan 1434 och 4319 mg/kg i profilen. Den största mängden P (2553 – 4319 mg/kg) fanns i de översta 40 cm i profilen. P var till största delen organiskt bundet (6679 % av Total-P). Resultaten visar att P extraherat med NaHCO3, NaOH och Residual-P utgjorde 95-97% av Total-P. Under vintern sjönk mängden Total-P och de största omvandlingarna verkade ske under våren och tidig sommar. pH varierade mellan 3,9 och 5,3. Vid en korrelationsberäkning mellan P fraktionerna visade det sig att P extraherat av NaHCO3 verkade övergå i Residual-P och i P extraherat med NaOH och vice versa. Likadant var det för P extraherat med HCl som verkade övergå i Residual-P och i P extraherat med NaOH och vice versa. Den här studien innefattade bara prover tagna i jord, därför skulle det vara mycket intressant att vidare undersöka in- och utflödet av P via tex den näringsrika Vinneå och via markvattnet. Växternas upptag skulle också vara intressant att undersöka. 3 Contents ABSTRACT........................................................................................................................................................... 2 SAMMANFATTNING (SWEDISH SUMMARY)............................................................................................. 3 CONTENTS........................................................................................................................................................... 4 INTRODUCTION................................................................................................................................................. 6 1. WETLANDS...................................................................................................................................................... 7 1.1 STREAMS AND RIPARIAN ZONE WETLANDS .................................................................................................... 7 1.2 WETLAND HYDROLOGY................................................................................................................................. 8 1.2.1 Climatic factors for Scandinavia .......................................................................................................... 9 1.3 WETLAND VEGETATION .............................................................................................................................. 10 1.4 HUMAN IMPACT ON RIPARIAN ZONE WETLANDS .......................................................................................... 10 2. WETLAND SOILS ......................................................................................................................................... 12 3. NUTRIENT UPTAKE BY PLANTS............................................................................................................. 14 3.1 PLANT NUTRITION ....................................................................................................................................... 14 3.2 FUNCTION OF THE ROOT SYSTEM ................................................................................................................. 14 3.2.1 Microorganisms in soil....................................................................................................................... 14 3.2.2 Root hairs and mycorrhizae................................................................................................................ 15 4. PHOSPHORUS ............................................................................................................................................... 16 4.1 PHOSPHORUS IN SOIL ................................................................................................................................... 16 4.1.1 Phosphorus in soil solution ................................................................................................................ 16 4.1.2 Phosphorus adsorption....................................................................................................................... 16 4.1.3 Phosphorus in minerals ...................................................................................................................... 17 4.1.4 Phosphorus in organic matter ............................................................................................................ 17 4.2 PHOSPHORUS RELEASE BY MICROORGANISMS AND ENZYMES...................................................................... 17 4.3 PHOSPHORUS-CYCLE IN WATERLOGGED SOILS ............................................................................................ 18 5. MATERIALS AND METHODS.................................................................................................................... 20 5.1. SITE DESCRIPTION ...................................................................................................................................... 20 5.1.1 History ................................................................................................................................................ 20 5.1.2 Streams influencing the site area........................................................................................................ 20 5.1.2.1. Water level fluctuation............................................................................................................... 21 5.1.3 Vegetation........................................................................................................................................... 22 5.1.4 Soil profile at the site.......................................................................................................................... 23 5.2 CLIMATE DURING THE STUDY PERIOD.......................................................................................................... 23 5.3. METHOD FOR PHOSPHORUS FRACTIONATION AND ANALYSIS ..................................................................... 24 5.3.1. Phosphorus fractionation and fraction description ........................................................................... 24 5.3.2. Phosphorus analysis .......................................................................................................................... 26 5.3.3. pH analysis ........................................................................................................................................ 27 5.3.4. Statistics............................................................................................................................................. 27 6. RESULTS AND DISCUSSION ..................................................................................................................... 28 6.1 PHOSPHORUS FRACTIONS AND PH ............................................................................................................... 28 6.1.1. Bicarbonate Organic and Inorganic Phosphorus.............................................................................. 29 6.1.2. Hydroxide Organic and Inorganic Phosphorus ................................................................................ 30 6.1.3. Total Organic and Inorganic Phosphorus......................................................................................... 31 6.1.4. pH ...................................................................................................................................................... 32 6.2. PHOSPHORUS FRACTIONS AND PH AT DIFFERENT DEPTHS AND DATES ........................................................ 33 6.2.1. Total Phosphorus............................................................................................................................... 33 6.2.2. Resin-extractable Phosphorus ........................................................................................................... 34 6.2.3. Bicarbonate-soluble Phosphorus....................................................................................................... 34 6.2.3.1. Bicarbonate-soluble Organic and Inorganic Phosphorus ......................................................... 35 6.2.4. Hydroxide-soluble Phosphorus ......................................................................................................... 36 6.2.4.1. Hydroxide-soluble Organic and Inorganic Phosphorus............................................................ 37 4 6.2.5 Hydrochloric acid-soluble Phosphorus .............................................................................................. 38 6.2.6. Residual Phosphorus ......................................................................................................................... 39 6.2.7. pH ...................................................................................................................................................... 40 6.3 CORRELATIONS ........................................................................................................................................... 41 6.4. GENERAL DISCUSSION ................................................................................................................................ 42 7. CONCLUSIONS ............................................................................................................................................. 44 7.1. CONCLUDING REMARKS ............................................................................................................................. 44 8. ACKNOWLEDGEMENTS............................................................................................................................ 45 9. REFERENCES................................................................................................................................................ 46 10. APPENDICES ............................................................................................................................................... 49 APPENDIX 1. TABLES A1-A36: RAW DATA ....................................................................................................... 49 APPENDIX 2. FIGURES A1-A5: PHOSPHORUS FRACTIONS AS A PERCENTAGE OF TOTAL PHOSPHORUS .............. 58 APPENDIX 3. FIGURES A6-A13: BICARBONATE AND HYDROXIDE INORGANIC AND ORGANIC PHOSPHORUS .... 61 APPENDIX 4. TABLE A37: WEATHER DATA ....................................................................................................... 65 APPENDIX 5. FIGURES A14-A19: PHOTOS OF THE SITE AREA ............................................................................ 66 5 Introduction Phosphorus (P) is a limiting factor for primary production (Horne & Goldman, 1994; Havlin et al., 1999). An unnatural load of P may disturb the balance in e.g. lake ecosystems. Natural lakes usually go through different trophic stages, from oligotrophic (low nutrient levels) to eutrophic (high nutrient levels, high primary production), during the succession phase. During ageing, lakes finally become overgrown with grass and trees and may turn into a marsh or even dry land. The rate of natural eutrophication depends on the mean depth of the lake and the size and fertility of the drainage basin. Human activity, such as lowering of the water level, discharge of sewage into lakes and excessive use of fertilisers in agriculture may increase this rate. The discharge of nutrients, whether they come from agriculture or from sewage (cultural eutrophication) disrupt the balance in the lake ecosystem and perhaps causes overproduction of algae, plants and fish (Horne & Goldman, 1994). This eventually leads to thick layers of organic matter at the bottom of the lake. The decomposition of this material causes oxygen depletion at the bottom of the water body and may cause dead lake bottoms and even fish death (http://www.naturvardsverket.se/index.php3?main=/document/lagar/bedgrund/sjo/sjo.html ). Blooms of blue-green algae are often the first sign of cultural eutrophication, and occur in late summer or autumn. These types of algae compete successfully with other species for nutrients and have developed other self-promoting features. They may regulate their position vertically during the day so that they always are at the most favourable position for sunlight and nutrition and also shade out other species. Some blue-green algae have the advantage of being able to fix atmospheric N2 gas. To avoid grazing by zooplankton, they produce toxins similar to those produced by many terrestrial plants. These toxins pose a great problem when the lake is used as water supply or for recreational purposes (Horne & Goldman, 1994). The use of P fertiliser has decreased recently in the Nordic countries. Even though Denmark uses the highest amounts, they do not have the largest losses. This is due to climatic factors such as temperature, which affects crop yield. Factors that affect nutrient losses include radiation and precipitation, which affect the annual runoff. These factors vary both on an annual and seasonal basis with, for instance, peak flows in spring and autumn. High runoff volumes may result in losses of high amounts of particulate and dissolved P. In spring, when the snow starts to melt, ground frost may prevent infiltration, leading to high erosion capacity of the snowmelt water. Other important factors affecting P losses include various agricultural structures, soils and topography (Rekolainen et al., 1997). Studies have been carried out on P cycling in cultivated soils and in freshwater lake ecosystems and the process involved are well understood, but less is understood about P cycling in freshwater wetlands (Amador, Richany & Jones, 1992). The present study was carried out within the EU project PROWATER with the aim of investigating what happens to P in a soil that is not cultivated and that is covered with vegetation all year round. Our hypothesis was that ‘soil phosphorus is transformed and its forms redistribute into various compartments depending on season’. The specific objectives of this study were to: 1) Determine total phosphorus status and distribution in the soil profile; 2) Break down total phosphorus into various compartments; 3) Evaluate impact of season on phosphorus dynamics. 6 1. Wetlands A wetland ecosystem requires that the land be kept wet during all or part of the year. This can be a result of high rates of water supply or/and water retention depending on the interaction between climate and landscape topography (Wheeler, 1999). Wetlands often form the boundary between terrestrial and aquatic ecosystems and include animal and plant communities of both systems. Therefore a small change in hydrology may cause a dramatic change in biota (Mitsch & Gosselink, 2000). In 1971, the importance of wetlands was internationally noted in the RAMSAR Convention on wetlands. According to this convention, wetlands are defined as ‘areas of marsh, fen, peat land 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 metres’ (http://www.ramsar.org/key_conv_e.htm, 2003). However there are many different types of wetlands with different characteristics caused by factors such as hydrology, salt or freshwater, climate, etc. Therefore various classification systems are used to describe wetlands, using different specific parameters such as vegetation, chemistry, hydrology, geology, etc. These systems reflect the interest of different researchers and the aims of their studies (Hughes & Heathwaite, 1995). Wetlands offer a variety of useful functions that are essential for animals and plants and for maintaining the quality of the environment. They function for example as wildlife habitats and dispersal corridors, they trap and deposit sediments and function as a nutrient source and sink. They provide riverbank stabilisation, counteract erosion and assimilate and immobilise environmental contaminants. From a societal point of view they are important for recreational and educational purposes. They are also economically important, as hay and peat may be harvested (Hughes & Heathwaite, 1995). 1.1 Streams and riparian zone wetlands All watercourses are similar in that they flow from higher altitudes toward lower ones. Water flow erodes the stream bank, releasing and transporting inorganic and organic materials and depositing them further downstream. There are basic types of stream reaches - rapids and slow-flowing stretches. Rapids, with channels of gravel, stones or bedrock, have very turbulent water flow and temporary sedimentation. Slow-flowing reaches have turbulent water flow only during floods. They have a higher continuous sedimentation of fine materials consisting of sand transported along bottoms, and suspend materials like silt, clay and organic matter. Vegetation along these stretches is completely different from that along rapids. (Nilsson, 1999). The land adjacent to a river, stream or other body of water is called the riparian zone. This zone is composed of mosaics of landforms and communities, of which riparian wetland is one type. These wetland ecosystems are unique because of their linear form and because they process large fluxes of energy and materials from the upstream system. The soil and soil moisture in these ecosystems are influenced by the adjacent water body through at least periodic flooding (Mitsch & Gosselink, 2000). The riparian zone changes along the course of a river system from its headwaters to its mouth through three major geomorphic zones: erosion, transport, and sediment deposition. The zone 7 of erosion is in the headwaters and upper reaches of low-order1 streams. Depending on the precipitation, there is a great variation in frequency and duration of the flood. Below the zone of erosion is the zone of sediment, nutrient and water transport. The extent of flooding depends on the precipitation and the size of the watershed. The zone of deposition is characteristic of high-order and low-gradient streams. Sedimentation is greater than transport and erosion and the valley slopes are gentle. This leads to broad floodplains and meandering stream channels. Seasonal flooding is characterised by one or a few long- or short-duration floods. It deposits fine sediments at the periphery of the floodplain and leaves the more coarse sediments in the channel (Mitsch & Gosselink, 2000). The slope of the stream and the elevation and area of the watershed determine the local flooding regime of the riparian zone. A stream with steep slopes floods with sharper peaks but less frequently than streams with gentle slopes (Mitsch & Gosselink, 2000). River topography also affects current velocity, soil conditions and microclimate, and is an important reason for vegetation heterogeneity (Nilsson, 1999). Both productivity and biodiversity in riparian zones are enhanced by the exchange of resources between riparian zones and the main channel (Figure 1) caused by seasonal floods. The composition and relative width of the vegetation zone differ between small streams and large rivers, due to differences in flood duration and channel topography (Nilsson, 1999). Riparian vegetation Provides terrestrial habitat Supplies detritus (energy) to stream Shades stream Controls primary production Food, rest and hiding for emergent adults Some eggs laid on foliage Food for aquatic invertebrates Alters water quality and quantity Controls stream temperature Habitat space & quality for aquatic invertebrates Growth rates & life cycles of aquatic invertebrates Figure 1. Example of functional relationship between riparian vegetation and stream aquatic communities (after Knight & Bottorff (1984) in Mitsch & Gosselink (2000)). 1.2 Wetland hydrology Hydrology is probably the single most important determinant of establishment and maintenance of specific types of wetlands and wetland processes. The first two important factors affecting the hydrology in wetlands are the climate and geomorphology of the 1 Rivers and streams may be classified by their order. Low-order streams are small and have no larger branches. When first-order streams join they become a second-order stream. The order will not increase if more first-order streams join. If second-order streams join, they become a third-order stream, and the process continues (Horne & Goldman, 1994). 8 landscape and basin. In wet or cool climates there are more wetlands than in hot or dry climates, as a result of higher precipitation in wet climates and lower evapotranspiration in cool climates. Flat or gently sloping landscape tends to have more wetlands than steep terrain (Mitsch & Gosselink, 2000). Each type of wetland is characterised by the hydroperiod, which is the seasonal pattern of the water level. The hydroperiod is the result of the water budget (sum of inflows and outflows) as influenced by physical character of the terrain and the closeness to adjacent water bodies. The major components of water budget in riparian wetland include precipitation, evapotranspiration, over-bank flooding and groundwater fluxes. The determination of water budget and hydroperiod may contribute to a better understanding of wetland function (Mitsch & Gosselink, 2000). The physiochemical environment of a wetland is directly modified by the hydrology, especially the oxygen availability and related chemistry such as nutrient availability, pH and toxicity. It is also influenced by hydrological inflows and outflows of nutrients, toxins, sediments, detritus, etc. The physiochemical environment may in turn affect hydrology, in that the build-up of sediments, for example, may affect the hydrological inflows and outflows. Changes in physiochemical environment may in turn have a direct impact on the wetland biota. Even a small change in water balance may affect productivity and species composition greatly. Some animal and plant species are adapted to anoxia and will benefit in these conditions. Microbes able to metabolise in anoxic conditions dominate the reduced sediments, while aerobic microorganisms survive in a thin layer of oxidised sediments and in the water layers if oxygen is present. When hydrological patterns remain similar from year to year, wetland biotic structure and functional integrity may persist for many years (Mitsch & Gosselink, 2000). 1.2.1 Climatic factors for Scandinavia The climate in Scandinavia is affected by the inflow of mild air from the Atlantic Ocean caused by the Gulf Stream. This leads to relatively mild winters compared to other parts of the globe at similar latitudes. The climate in Sweden is highly seasonal. In southern Sweden, snowfall may occasionally occur but may also be absent or replaced by rainfall in any part of the winter. In central and northern Sweden, a lasting snow cover persists for 4-6 months. Ice and snowmelt usually occur in April or early May, as does the seasonal ground frost which in most winters occur all over Sweden (Sjörs, 1999). Precipitation in Sweden, which is highest in the south-west, is mainly caused by moist air from the Atlantic. Rainfall is often high in July and August and often also in the autumn, and low in the spring and early summer. However, this is rather irregular and may vary from year to year, which may lead to a large seasonal river discharge fluctuation (Nilsson, 1999). Evaporation depends on the summer heat and the length of the warm period, which is longer in the south and is thus greater in summer. However the remaining surplus of water varies more than the precipitation itself, leading to different groundwater conditions (Sjörs, 1999). There is a distinct zonation of the temperature climate as it affects the vegetation. This is mainly due to stronger south to north temperature differences in spring and autumn than in summer, which leads to different lengths of the climatic growing season. In the Kristianstad area, the growing period is about 210 days, whereas in the north it is between 100-150 days 9 (Sjörs, 1999). The growing season is defined as the period between the last killing frost of spring and the first killing frost of autumn, when the daily mean air temperature is above +5oC (www-markinfo.slu.se/sve/klimat/vegper.html; www.bartleby.com/65/gr/growings.html). 1.3 Wetland vegetation Wetland plant composition and community boundaries in floodplains are dependent on the amplitude of the flooding. When flooded, the soil may be just saturated or wetland plants may be completely submerged. When the water level is low, it may be just below the soil surface or well below the rooting zone. The impact these changing conditions have on plants and plant communities depends on their magnitude and duration, as well as the identity and stature of the plant species concerned (Wheeler, 1999). However, the soil moisture may be a more important factor for plant growth than the position of the watertable. Due to different soil types, the moisture content of the upper soil layer at any low water level can vary between wetlands. This is mainly because of different capillary properties and removal of evapotranspiration (Wheeler, 1999). Plants colonising wetlands show a considerable variation in their tolerance of, and adaptation to, different water regimes and duration of flooding or droughts. Some plants have developed different strategies to avoid the effect of waterlogging or drought, for example by surviving as seeds or other perennating organs such as roots, tubers or rhizomes. Another way to survive in wet conditions is to develop anatomical structures (lacunae, aerenchyma and respiratory roots). These are used to maintain aerobic respiration by assisting the diffusion of atmospheric oxygen to the underground parts of the plant. Some plants have adapted to these conditions by accelerated shoot growth, to extend above the level of flooding. With this in mind, three broad types of wetlands can be recognised from a plant ecology point of view: Permanent wetlands - low water level fluctuations do not drive floristic change. Seasonal wetlands - fluctuation amplitude of the watertable is so great that only opportunistic plants, if any, colonise the wetland. Fluctuation wetland - great long-term watertable fluctuations and duration, causing a change in composition of perennial plants or periods when perennial plants cannot grow (Wheeler, 1999). Different vegetation types and contrasting habitat conditions can vary greatly within a single wetland site. Peat as a soil substrate can accumulate where the watertable remains close to the soil surface much of the year, especially in temperate and boreal regions. Sites strongly influenced by fluctuating watertables may have a main composition of minerals because of alluvial depositions and the prevention of peat accumulation caused by low water levels (Wheeler, 1999). As a result of climatic factors and the fact that the watercourse becomes larger downstream, the plant community composition changes dramatically from the upstream to the downstream reaches. Watercourses play a large role as dispersal corridors, which lead to a distribution of species beyond their normal range (Nilsson, 1999). 1.4 Human impact on riparian zone wetlands When people started to optimise their farming, there was no use for wetlands any more. Farmers were encouraged by the government to drain or fill this wet non-productive land so it could be used as farmland or used in other ways, as the only policy for managing wetlands. 10 This led to a dramatic decrease in wetlands in a short period of time (Mitsch & Gosselink, 2000). When an wetland area is drained, the water is led away and the hydrology of the area is modified. The purpose of drainage is to dry the land out for agricultural or industrial use, although ditches are sometimes installed as transportation canals across wetlands. Roads may also be built across wetlands, which alters the hydrology, promotes sediment loading and may destroy the wetland totally (Mitsch & Gosselink, 2000). Surface peat mining in wetlands is common in several European countries. Peat is used as fuel in electric power plants, as potting compost and garden soil, but also as a filtering medium to remove toxic materials and pathogens from wastewater (Mitsch & Gosselink, 2000). The great loss of wetlands in the world and the recognition of wetland values have stimulated the restoration and creation of these systems, which may be carried out in several ways. An existing wetland may be restored from a condition caused by human activities or it may be altered on purpose to increase one or several functions. Conversion of previous upland or shallow-water areas may create new wetlands (Mitsch & Gosselink, 2000). These wetlands are often used to remove contaminants and pollution from wastewater (Maltby, 1986; Mitsch & Gosselink, 2000). Natural wetland usually receives non-polluted water. If a wetland receives polluted water from local or upstream runoff, or if sewage water is led through such wetland, the quality of the water flowing out of the wetland may change. However, the polluted water may in turn change the wetland by eutrophication and altered biological composition. If toxic compounds reach the wetland, biological life may be destroyed (Lönngren, 1995; Mitsch & Gosselink, 2000). Sweden has about 10 million hectares of wetlands, or about 25% of the national land area. Therefore Sweden is one of the top ten wetland-richest countries in the World. However about 25% of the original wetlands in Sweden have disappeared through drainage since the end of the Nineteenth Century (Naturvårdsverket & SCB, 2000). Riparian zones in Sweden have been used by humans for a long time. The lower parts of the zones have been used for haymaking by harvesting helophytes such as Carex and Equisetum, whereas the upper parts of the zones, from which trees and shrubs have been cleared, have been used as meadows. The meadows were fertilised by annual flooding and usually harvested each year (Nilsson, 1999). 11 2. Wetland soils Biogeochemical cycling, chemical transformation and transportation in ecosystems involve several chemical, physical and biological processes. These processes are markedly influenced by waterlogged conditions (as mentioned in 1.2). Biogeochemical cycling in wetlands may be divided into two main systems - the exchange of chemicals between the wetland and its surroundings; and the cycling within the wetland through various transformation processes. If the wetland has no or little exchange with its surroundings, as for example ombrotrophic bogs, the system is considered closed. Wetlands adjacent to rivers and lakes may, on the other hand, have abundant exchange with their surroundings and are considered open. Even if few transformation processes are unique to wetlands, certain transformation processes tend to be more dominant in wetlands than in either upland or deep aquatic ecosystems, due to permanent or intermittent flooding (Mitsch & Gosselink, 2000). Wetland soils may be divided into organic soils and mineral soils, the latter containing less than 20-35% organic matter (dry weight). Mineral wetland soils usually have a soil profile made up of horizons. Organic soils differ further from mineral soils in several physiochemical features (Table 1). The porosity in organic soils is generally 80% pore space or more, whereas mineral soil porosity ranges between 45-55% pore space. The porosity affects the bulk density, which is defined as the dry weight of soil materials per unit volume. Organic soils have low bulk density due to high porosity, usually ranging between 0.2-0.3 g/cm3, whereas the bulk density of mineral soils ranges between 1.0-2.0 g/cm3. Both mineral soils and organic soils have a wide range of possible hydraulic conductivity values. Organic soils may hold more water due to high porosity, but do not necessarily allow water to pass through more rapidly compared with mineral soils. Minerals soils often contain more nutrients than organic soils. The nutrient content in organic soils may be bound in organic forms and unavailable to plants (Mitsch & Gosselink, 2000). Table 1. Comparison of mineral and organic soils in wetlands, after Mitsch & Gosselink, 2000 Parameter Organic content (%) Organic carbon (%) pH Bulk density Porosity Hydraulic conductivity Water holding capacity Nutrient availability Cation exchange capacity Mineral soil Less than 20-35 Less than 12-20 Usually around neutral High Low (45-55%) High (except for clays) Low Generally high Low, dominated by major cations Organic soil Greater than 20-35 Greater than 12-20 Acid Low High (80%) Low to high High Often low High, dominated by hydrogen ions Organic wetland soils consist mainly of plant residuals in various stages of decomposition. The organic matter is accumulated because of the anaerobic conditions due to waterlogging (Mitsch & Gosselink, 2000). Organic matter can be divided into non-humic and humic substances. The non-humic substances consist of amino acids, proteins, carbohydrates, fats, waxes, alkanes and low-molecular-weight organic acids. Humic substances comprise the majority of organic matter and are chemically complex compounds with high molecular weight. Non-humic substances are decomposed faster than humic substances. The chemical composition of organic matter can vary from soil to soil, but is in general approximately 50% C, 5% N, 0.5% P, 0.5% S, 39% O and 5% H (w/w). Some functional groups in humic substances are carboxy, phenolic, hydroxyl, alcohol hydroxyl, and carbonyl groups (Barber, 1995). Two important characteristics of organic soils are the plant origin and degree of decomposition. Many properties such as bulk density, cation exchange capacity, hydraulic 12 conductivity and porosity are often dependent on these characteristics. The origin of the plant residuals varies from mosses to herbaceous materials and wood and leaf litter. The herbaceous material may be sedges like Carex and Cladium or reed grass Phragmites, or other non-grass or non-sedges such as Typha. During decomposition, the plant material changes both physically and chemically until it does not resemble the original material. As the decomposition proceeds, the bulk density increases, hydraulic conductivity decreases and the amount of fibric particles larger than 1.5 mm decreases. The relative amount of waxes and lignin increases due to a decrease in plant pigments and cellulose, which are more easily decomposed (Mitsch & Gosselink, 2000). Flooded mineral soils develop certain characteristics called redoximorphic features. These features are formed by reduction, translocation, and/or oxidation of iron and manganese oxides. It is microorganisms that cause these features to develop, and there are three obligate conditions determining the rate of development. First, there must be continuous anaerobic conditions. Secondly, there must be a temperature (normally above +5oC) sufficient for biological processes. Thirdly, the microbes need an organic substrate to support their activity. Under aerobic conditions, iron and manganese are in the solid forms Fe3+ and Mn3+ or Mn4+ and colour the soil red and black respectively. Iron and manganese reduce to their soluble forms Fe2+ and Mn2+ when the soil is waterlogged and anaerobic conditions occur. When the soil becomes aerobic again, chemosynthesising bacteria oxidise iron and manganese from their soluble forms to their insoluble forms. This also occurs non-biologically at neutral or alkaline pH. When soluble, these ions may leach and the soil regains its natural colour of grey and black depending on the colour of the parent material. In a similar way, clay may selectively deplete along root channels to redeposit as a clay coating on soil particles further down. In some wetlands an oxidised rhizosphere may occur. This is caused by the capacity of many hydrophytes to transport oxygen from the stem above ground to the roots below. The oxygen not needed for root metabolism diffuses into the surrounding soil. In this oxidised zone, soluble iron may oxidise into its solid form and deposit around small roots (Mitsch & Gosselink, 2000). 13 3. Nutrient uptake by plants 3.1 Plant nutrition Plants get the raw material for their maintenance and growth from the soil and the atmosphere. Almost all plants can transform CO2 and H2O and sunlight into organic compounds for their energy source. They use inorganic compounds from their environment to synthesise the vitamins and amino acids they require. Over 60 chemical elements have been identified in plants, but only a few are essential for them to complete their lifecycle. Today seventeen such elements have been identified and are divided into micronutrients and macronutrients. The micronutrients are required in very small amounts (less than 100 mg/kg of dry matter) whereas macronutrients are required in large amounts (1000 mg/kg of dry matter or more) (Raven, 1999). Phosphorus (P) is considered to be a macronutrient. The most essential function of phosphorus in plants is energy storage and transfer, but it also acts as an important structural component of nucleic acids, coenzymes, nucleotides, phosphorus proteins, phospholipids and sugar phosphate (Havlin et al., 1999; Raven, 1999). Plants contain about 0.1 to 0.5% phosphorus (Havlin et al., 1999). The main P source for plants is the two inorganic forms of orthophosphate ions, H2PO4- and HPO42-. The uptake of HPO42- is slower than the uptake of H2PO4-. Plants can also absorb certain soluble organic phosphates such as nucleic acids and phytin, but this P source is limited, especially to higher plants, in the presence of an active microbial population which decomposes these compounds rapidly (Havlin et al., 1999). 3.2 Function of the root system Roots have many tasks and their main functions are absorption, anchorage, storage and conduction. Most of the essential nutrients are absorbed via roots. Several kinds of root system can be recognised, e.g. a taproot system and a fibrous root system. The taproot system has one taproot, which grows directly downwards, giving rise to lateral roots. Fibrous root systems develop from many adventitious roots raised from the stem, and produce lateral roots. Several factors, such as moisture, temperature and soil composition, determine how deep and how far laterally the root system grows (Raven, 1999). 3.2.1 Microorganisms in soil The rhizosphere is the layer of mucigel covering the epidermis in the absorptive part of some roots and the soil particles bound to it. This layer provides an environment for a variety of microorganisms and may affect ion availability to the root. The rhizosphere may also, in the short-term, prevent the root from drying out (Raven, 1999). One major reason for the high microbial activity in the rhizosphere may be the organic exude from the root, consisting of root cap cells, old root hairs etc., which serves as an energy source (Barber, 1995). The general breakdown of organic matter in soil is generated by heterotrophic bacteria, fungi and actinomycetes. Under anaerobic conditions, bacterial decomposition dominates (Brady & Weil, 1996). Soil bacteria are divided in groups depending on their oxygen requirement, nutritional pattern and symbiotic relationship (Donahue et al., 1983). Autotrophic bacteria obtain their energy from sunlight (photoautotrophs) or from oxidation of inorganic constituents (chemo- 14 autotrophs), for example iron and sulphur. They obtain most of their carbon from CO2 and carbonates. These bacteria are not a large group but they play an important role in controlling nutrient availability to higher plants. Heterotrophic bacteria, which represent the biggest group of soil bacteria, obtain their energy and carbon from organic matter in the soil (Donahue et al., 1983; Brady & Weil, 1996). Soil bacteria can digest most naturally-occurring materials and also a diversity of toxic element such as insecticides and other organic toxins, due to their broad range of enzymatic capability. Bacteria also dominate several basic enzymatic transformations, for example the oxidation and reduction of selected chemical elements in soil. Some chemoautotrophic bacteria obtain their energy from such oxidations. Anaerobic and facultative bacteria reduce a number of substances other than oxygen gas. Many of these biochemical reactions play a great role for environmental quality, as well as for plant nutrition (Brady & Weil, 1996). Actinomycetes are classified in the kingdom Monera, as are bacteria, and they are generally aerobic heterotrophs. They get their energy from decomposing organic materials but also from compounds supplied by certain plant species in a parasitic or symbiotic relationship. Many actinomycetes species produce antibiotic compounds that kill other microorganisms. Actinomycetes are numerous in soils high in humus, for example old meadows and pastures. They are sensitive to acidic soil conditions and optimum pH value is between 6.0-7.5. Actinomycetes often dominate the late stages of decomposition because they also reduce resistant compounds such as lignin, cellulose, and phospholipids (Brady & Weil, 1996). Fungi represent a diverse group of heterotrophic and generally aerobic microorganisms. However some fungi tolerate rather low oxygen concentrations found in wet or compacted soils. Fungi may be divided in three groups, yeasts, moulds and fungi. Yeasts, which are single celled-organisms, live mostly in waterlogged, anaerobic soils. Moulds and fungi are both filamentous characterised by hyphae. Moulds play a greater role in decomposing organic matter than do fungi. They develop vigorously in acid, neutral and alkaline soils and are therefore abundant in acidic soils where both bacteria and actinomycetes are few. Although fungi are not as widely distributed as moulds, they are important in the breakdown of woody tissue and the formation of symbiotic relationships (mycorrhizae) with plants (Brady & Weil, 1996). 3.2.2 Root hairs and mycorrhizae To obtain better nutrient and water uptake, roots can develop root hairs or live in symbiosis with fungi (mycorrhizae). Root hairs are tubular lateral extensions of the epidermal cells of the root. They increase the absorptive surface of the root by a factor of 2 to 10 (Barber, 1995). Root hairs are relatively short lived but new hairs are developed almost at the same rate as the old ones die (Raven et al., 1999). Mycorrhizae have a mutualistic symbiosis between fungi and root. The fungi provide the root with water and some essential elements, especially phosphorus. The fungi increase the P availability to plants, not only by extension of hyphae into the soil, but also through the secretion of organic acids (Stevenson, 1986). The root provides the fungi with carbohydrates and vitamins essential for their growth. Mycorrhizae can be found in most soils in symbiosis with most plant species. Mycorrhizae can be classified into five groups: ecto-, endo-, ericoid-, arbutoid and orchidaceous. The major groups are endo- and ecto-mycorrhizae (Barber, 1995; Raven et al., 1999). 15 4. Phosphorus 4.1 Phosphorus in soil Phosphorus occurs in both inorganic and organic forms in soil. The content of P in the soil ranges between 100 and 2 500 kg/ha, with an average of 1000 kg/ha in the top 20 cm (Mitchell et al., 1986). Phosphorus in soil may be divided into four main categories: (1) P as ions and compounds in the soil solution; (2) P adsorbed on the surface of inorganic soil constituents; (3) P minerals, both crystalline and amorphous; and (4) P as a component of soil organic matter (Barber, 1995). 4.1.1 Phosphorus in soil solution The concentration of P in soil solution varies among soils, but the concentration required by plant ranges between 0.003 and 0.3 ppm and depends on the type of vegetation. As roots from the soil solution absorb P, additional P is transported toward the roots via diffusion and mass flow. Soluble inorganic P is in the form of orthophosphate, H2PO4- and HPO42- and the predominant form depends on the pH (Table 2). Normally soil pH ranges between 4.4 and 8.5 and at pH 7.2 the amounts of the two phosphate ions are generally equal (Barber, 1995; Havlin et al., 1999). As much as half the phosphate in soil solution may be as soluble organic compounds, especially in soils with a high content of organic matter (Barber, 1995). Table 2. Predominant forms of soluble inorganic phosphorus depending on pH (after Barber, 1995) pH value pH 7.2 pH< 7.2 pH> 7.2 Predominant form H2PO4- = HPO42H2PO4- < HPO42H2PO4- > HPO42- 4.1.2 Phosphorus adsorption Surface adsorption and precipitation reactions are collectively called P fixation or retention. Inorganic P that is not absorbed by plants or by microorganisms can be adsorbed to mineral surfaces (labile P) or precipitate as secondary P compounds. The most important factor affecting the extent to which P is fixed is pH. In soils with a pH of 7.2, inorganic P precipitates as Ca-P secondary minerals and/or is adsorbed to clay minerals and CaCO3. In soils with a pH<7.2, inorganic P is adsorbed to clay minerals and Fe/Al-oxides and/or is precipitated as Fe/Al-P secondary minerals (Barber, 1995; Havlin et al., 1999). Hydroxy minerals and Al and Fe oxides are primarily involved in the adsorption of inorganic P in acidic soils. Although both positive and negative sites exist, positive sites dominate and give a net positive charge. These sites attract anions such as H2PO4- and HPO42-. When adsorbed, OH- and OH2+ sites on the Fe/Al-oxide interact with the P ion. When the P ion is bound through one Al-O-P bond, the ions are considered labile and are desorbed readily to the soil solution. When two Al-O bonds occur with one P ion, the orthophosphate is considered non labile and desorption is more difficult (Havlin et al., 1999). Both Fe/Al-oxides and clay are capable of adsorbing large amounts of P in soil solution. However, the amount of P adsorbed depends on the amount of clay and Fe/Al-oxides in soils 16 and the pH. Adsorption of P by Fe/Al-oxides decreases with increasing pH. Bloom (1981) suggests that Al-substituted peat has a high affinity for the adsorption of phosphate ions in the pH range 3 to 6. Phosphorus may also compete with both inorganic and organic anions for bonding sites. Anions such as H3SiO4-, SO42-, OH-, COOH- and MoO42- can be competitive with P. Humus acid may also compete for bonding sites on Fe/Al-oxides and create a protective cover, thereby decreasing P adsorption. Organic anions such as citric oxalate, tartate and malate may form stable chelate complexes with Fe and Al ions from Fe-P and Al-P complexes, and thereby solubilise P (Havlin et al., 1999). Anaerobic conditions occur when the soil moisture increases up to the extent of flooding. This results in reduction of FePO4 to Fe3(PO4)2, which is soluble. Similar reactions occur with Mn3(PO4)4 which reduces to soluble Mn3(PO4)2 (E. Otabbong, pers. comm. 2003). 4.1.3 Phosphorus in minerals Many minerals in the soil may be potential P sources, particularly minerals of P combined with calcium, aluminium and iron (Barber, 1995). Some secondary minerals of P are wavellite [Al3(PO4)2(OH)3 x 5H2O], vivianite [Fe3(PO4)2 x 8H2O], dufrenite [FePO4 x Fe(OH)3] and variscite [Al(PO4) x 2H2O] (Stevenson, 1986). Most rocks contain P (P2O5) in amounts of 0.15-0.2%, predominantly in the form of silicate and apatite minerals, which are relatively stable in surface environment. The local availability of P from rocks depends on three factors. Firstly, the soil may contain uncommon rocks that contain high amounts of P, like basaltic volcanic rocks and P-rich sedimentary rocks. Secondly, rocks may be more or less easy weathered. Thirdly, the environment itself in terms of e.g. climate or water acidity may affect the P availability (McKelvey, 1973). 4.1.4 Phosphorus in organic matter Organic soil P varies typically between 15 and 80% of the total P in most soils. The distribution of P with depth also varies among soils. Inositol phosphate, phospholipids and nucleic acids are esters of orthophosphoric acid (H2PO4-), of which most organic P compounds consist. Of the total P, the approximate proportion of inositol is 10-50%, phospholipids 1-5% and nucleic acid 0.2-2.5%. Phospholipids and nucleic acids are broken down more quickly than inositol, hence the large difference in concentration. Microbial residues, which contain stabile esters, are believed to make up the remaining P compounds (Barber, 1995; Havlin et al., 1999). 4.2 Phosphorus release by microorganisms and enzymes Immobilisation and mineralisation occur simultaneously in soil and may be described as follows: Mineralisation Organic P Immobilisation Inorganic P (H2PO4-/HPO42-) Microorganisms mineralise P through the degradation of organic residues into other organic compounds which release inorganic P. However, some organic compounds, such as humic acids, are resistant to microbial degradation (Havlin et al., 1999). Phosphatase is an important enzyme that catalyses the mineralisation of organic P into inorganic P by the reaction: R-PO4- + H2O → HPO42- + ROH (Stevenson, 1986; Havlin et al., 1999). Phosphatase may be present both intracellularly and in the soil solution after being released by the lysis of microbial cells (Stevenson, 1986). 17 Microorganisms may also immobilise available phosphates into cellular material and promote the solubilisation of fixed or insoluble mineral forms of P, for example through the production of chelating agents. Organic chelates form complexes with Ca, Fe or Al and thereby release the phosphate in water-soluble forms as follows: CaX2 x 3Ca(PO4)2 + chelate → soluble PO42- + Ca-chelate complex (where X = OH or F) and Al(Fe) x (H2O)3(OH)2H2PO4 + chelate → soluble PO42- + Al(Fe)-chelate complex Total organic P is, in most soils, highly correlated with soil total organic C. Therefore, mineralisation would be expected to increase with increasing total organic C, in the way nitrogen does2. However, the situation for P is different because of the fact that total organic P is present in compounds with different solubilities. Moreover, organic P can be bound by the soil and is thereby less accessible to microorganisms. When organic P decreases, P immobilisation increases. The C/P ratio of the decomposition residues regulates the predominance of P mineralisation over immobilisation. Other factors affecting the quantity of P mineralisation/immobilisation are temperature, moisture, aeration and pH (Stevenson, 1986; Havlin et al., 1999) Table 3. Phosphorus mineralisation and immobilisation (after Stevenson, 1986) C/P ratio <200 200-300 >300 Mineralisation/Immobilisation Net mineralisation of organic P No gain or loss of inorganic P Net immobilisation of inorganic P 4.3 Phosphorus-cycle in waterlogged soils The phosphorus cycle in wetland soil is shown in Figure 2 (after Mitch and Gosselink, 2000). When soils are inundated with water, reduced (anaerobic) conditions usually occur due to oxygen diffusing much more slowly through water-filled pores than air-filled pores. However, there usually is an oxidised (aerobic) soil layer, sometimes only a few millimetres thick, at the soil-water interface. The thickness of this layer is determined by the oxygen transport rate over the atmosphere-surface water interface, the amount of oxygen-consuming microorganisms present, the oxygen production by algae within the free water and the mixing of the water caused by convection currents and wind action. There may also be transport of excess oxygen by wetland plants to their roots. This oxidised layer is often important for the chemical transformation and nutrient cycling that occur in wetlands. Particulate organic P from plant and microbial residues may transform into soluble organic P (SOP) and further into inorganic soluble P in both the free water and the oxidised and reduced soil layers. In the oxidised soil layer, however, iron may be oxidised from its soluble form Fe2+ to its insoluble form Fe3+ and precipitate P as FePO4 . Manganese also behaves in this way and precipitates P as Mn3(PO4)4. In the anaerobic layers, the reaction proceeds in the opposite direction and releases P again. Inorganic P and soluble organic P may diffuse 2 If the C/N ratio is <20-25 there is a net mineralisation of organic N. If the C/N ratio is >2025 there is a net immobilisation of inorganic N (Persson, 2003). 18 upwards to the oxidised layer and may also diffuse to the free water. However, inorganic soluble P from the free water may precipitate in the oxidised soil layer. Inflows (runoff, tides etc.) Air Surface water Oxidized soil layer Reduced soil layer Plant/microbial uptake Particulate organic P Particulate organic P Sedimentation SOP PO43- SOP PO43- Adsorption Precipitation Upward diffusion Anaerobic Anaerobic release of of PP release SOP PO43- Particulate inorganic P including Ca-P, Al-P, Fe-P Plant uptake Figure 2. Phosphorus transformations in wetlands. SOP indicates soluble organic phosphorus (redrawn from Mitsch and Gosselink, 2000). 19 5. Materials and methods 5.1. Site description 5.1.1 History The Kristianstad plain was covered with ice during the last glacial period. About 13 000 years BP, the ice started to melt and the plain was inundated. The sea level was about 50 m above the current level. As the ice melting proceeded northwards, the suppressed earth crust started to rise and the plain was drained and the sea level sank 30 m below the current sea level. The area around Lake Hammarsjön became covered with a forest of alder (Alnus glutinosa) (Magnusson & Vägren, 1994). During the period 7 500- 4 000 years BP the sea level rose and fell several times, and the alder forest was immersed. Some of these 7 500-year-old alder logs are still found today on the bottom of Lake Hammarsjön. The last sea level rise took place about 4 000 years BP and the watertable reached 8-10 m above the current sea level. When the water retreated, lakes were formed. The strong sea currents created a bank of sand, which in turn made a large lagoon. The lagoon was overgrown with vegetation and gradually a large area of marsh was created and only a few open water surfaces were left (Magnusson, 1981). Today, the area around Kristianstad holds one of the largest marsh areas in Sweden, in spite of the fact that the marsh has been altered during the past 400 years. These alterations were due to human desire to control this ‘water-sick’ land and use it as arable land. Up to the 1700s, the marsh was only used for haymaking and as grazing land for animals. Later, rivers and streams were straightened, areas were filled with rocks, and ditches were made for drainage. Lakes were drained and the river Helgeå was regulated through a power plant dam further up in the basin. Sewage from fast-growing villages, lowering of the watertable in the river-lake system and regulation of the river Helgeå all contributed to the eutrophication of Lake Araslövssjön and Lake Hammarsjön. Today efficient sewage treatment plants are minimising the nutrient supply to these lakes (Magnusson, 1981). The marsh that was left untouched forms an internationally valuable area, included in the wetlands list of the Ramsar Convention. This marsh area of ~ 5 500 hectares represents the lower part of the river Helgeå from the village Torsebro to the Baltic Sea at Åhus. The riparian zone meadows are the most valuable areas, which have been harvested, grazed and flooded regularly over a long period of time. This has created a specialised flora and fauna adapted to these conditions. These meadows are valuable resting sites for migratory birds such as ducks, geese and waders. If the regular harvesting and grazing ceases, the area will become overgrown and high herbs, reeds, shrubs and trees will take over (Cronert, 1996). 5.1.2 Streams influencing the site area The stream Vinneå with its length of 33.5 km has its origin in Hässleholm municipality on the Nävlinge ridge and stretches out to the Kristianstad plain in Kristianstad municipality. On the Nävlinge ridge, forest and pasture dominate and the stream meanders. When the stream has passed the village of Vinlsöv, the nature of the surrounding area changes into farmland on the Kristianstad plain and the river is straightened and remains so until it reaches its outflow in the river Helgeå. The river Vinneå basin is about 197 km2 in area and is depicted in Figure 3. About 35% of this area consists of farmland, located mainly on the intensively farmed Kristianstad plain. Forest and pasture area constitute 44% and 9% respectively, located 20 mainly on the Nävlinge ridge. Built-up areas and remaining land constitute 3% and 9% respectively (Fristedt, 1999). An air photo of the sampling area is shown in Figure A14. N Figure 3. Drainage area of stream Vinneå (Lantmäteriverket, ur GSD Röda kartan). The star indicates the sampling site. 5.1.2.1. Water level fluctuation The water in the river Helgeå flows slowly due to the low fall of about a couple of metres from Torsebro to the sea. The water amplitude varies during the year between 1.3 m above sea level to 0.1 m below the sea level, with its peaks after snowmelt in spring and after heavy rain in late autumn (Cronert, 1996). Water level fluctuation was not monitored during the sampling period for the stream Vinneå. However Kristianstad municipality continuously monitors the water level fluctuations in the river Helgeå in Kristianstad town and the water level fluctuations in the Baltic Sea at Åhus (Figure 4). The stream Vinneå is a tributary to the river Helgeå, and is thereby influenced by 21 m above a fix sealevel the water level fluctuations of the Helgeå, which may cause flooding in the adjacent area (Figure A15-A18). 0,8 0,6 0,4 0,2 0 -0,2 -0,4 August 2000 September 2000 River Helgeå October 2000 November 2000 December 2000 January 2001 February 2001 March 2001 April 2001 Baltic sea Figure 4 . Water level fluctuations of the river Helgeå in Kristianstad town and of the Baltic Sea at the mouth of the river Helgeå in Åhus. (http://www.weather.vattenriket.kristianstad.se/cgi-win/vader.exe), Zero is in Åhus = +0.05 m above a standard sea level in RH70 (Karin Magntorn; Barry Broman, pers. comm. 8/12/2004). 5.1.3 Vegetation The sampling site was a meadow covered mainly by Deschampsia cespitosa spp. cespitosa and Alopecurus pratensis. In the wetter parts Juncus effusus was found. This meadow is not fertilised directly. It is harvested in years when it is dry enough to use agricultural machines, and is sometimes grazed by cattle. 22 5.1.4 Soil profile at the site The soil in the site area is classified as a Eutic Histosol, according to Troedsson and Wiberg (1986). The soil profile at the site is shown in Table 4. Table 4. Soil profile at the site (Otabbong & Fristedt, 2005) Depth (cm) 0-30 pH (H2O) 5.41 Bulk density (gcm-3) 0.27-0.35 30-60 4.47 0.15-0.2 H5- Moderately decomposed peat, which when squeezed releases very small amounts of amorphous granular peat escaping between the fingers. The structure of the plant remains is quite indistinct although it is possible to recognize certain features. The residue is very pasty. 60-90 4.79 0.09-0.12 H2- Almost entirely undecomposed peat which when squeezed releases clear or yellowish water. Plant remains still easily identifiable. The plant remains are yellowish. Degree of humification (H) according to von Post (1922) H7- Highly decomposed peat. Contains a lot of amorphous material with very faintly recognizable plant structure. When squeezed, about ½ of the peat escapes between the fingers. The water is dark and almost pasty. 5.2 Climate during the study period Precipitation and air temperature dynamics for the sampling period are depicted in Figure 5. The chart shows an approximately 270-day-long vegetative period in the year 2000, starting in the middle of March and ending in the middle of December. The winter lasted for about 3.5 months and the vegetative period started again in the beginning of April 2001. The annual precipitation and air temperature for 1998 – 2000 is shown in Table 5. During those years the amount of precipitation was between 697 and 955 mm. The number of days with precipitation decreased from 162 in 1998 to 148 in 2000. The air temperature increased during these three years from 8.3 in 1998 to 9.7 in 2000. Table 5. Precipitation and air temperature for the sampling area during the three years, including the first study year (2000) (http://www.weather.vattenriket.kristianstad.se/cgiwin/vader.exe) Year 1998 1999 2000 Precipitation (mm) Precipitation Number of days with precipitation 831 162 955 154 697 148 Air temperature (◦C) Maximum Average Minimum temperature temperature temperature 26.9 8.3 -11.9 29.9 9.1 -13.7 32.9 9.7 -13.9 The monthly precipitation and average air temperature for the sampling period close to the site are presented in Table A37. The precipitation during the sampling period ranged between 20 and 122 mm. The lowest precipitation period was during February and March in 2001, 23 45 1 40 35 2 4 3 30 5 20 10 temp limit for growing period 30 0 f reezing point -10 20 ◦ -20 15 precipitation 9-7 2001 24-7 2001 9-6 2001 24-6 2001 25-5 2001 10-5 2001 25-4 2001 10-4 2001 26-3 2001 11-3 2001 9-2 2001 24-2 2001 25-1 2001 10-1 2001 26-12 2000 11-12 2000 26-11 2000 11-11 2000 27-10 2000 27-9 2000 12-10 2000 12-9 2000 28-8 2000 13-8 2000 29-7 2000 14-7 2000 29-6 2000 14-6 2000 30-5 2000 -50 15-5 2000 0 30-4 2000 -40 15-4 2000 5 31-3 2000 -30 1-3 2000 10 16-3 2000 Precipitation (mm) 25 Air temperatur ( C) with about 20 mm for each month. The wettest month was June 2000, with a precipitation amount of 122 mm, but during the autumn (September – November) the amount of precipitation varied between 61 and 95 mm. The average air temperature during the summer (June – August) 2000 ranged between 15.5 and 16.8 ◦C and the autumn temperature ranged between 7.6 and 13.0 ◦C. The winter (December 2000- March 2001) had an average air temperature ranging between 0.2 and 3.4 ◦C. From April to 5th June, the temperature ranged between 9.3 and 13.3 ◦C. temp Figure 5. Dynamics of precipitation and air temperature over the sampling period close to the sampling site (N 56◦ 02’ 05,0825’, O 14◦ 09’ 11,1474’), where 1, 2…5 =dates of sampling occasions (1=5th September 2000, 2=8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5=5th June 2001) (http://www.weather.vattenriket.kristianstad.se/cgi-win/vader.exe). 5.3. Method for phosphorus fractionation and analysis 5.3.1. Phosphorus fractionation and fraction description To separate P forms from the total P content, a sequential fractionation was conducted according to the method established by Hedley et al. (1982) and modified by Otabbong & Persson (1994). The fractionation was conducted in four stages where each stage was given a P fraction name depending on the agent used (resin (an anion exchanger), bicarbonate, hydroxide and hydrochloride) to extract P from the soil. The fractions in this study are therefore referred to as Resin-P, Bicarbonate-P, Hydroxide-P and HCl-P. To obtain the fraction referred as Residual-P in this study, Resin-P, Bicarbonate-P, Hydroxide-P and HCl-P were subtracted from Total-P. As reviewed by Otabbong & Persson (1994), Resin-P and Bicarbonate-P consist of inorganic P and organic P and are labile. When adsorbed to surfaces of crystalline compounds, sesquioxides and carbonates, P is readily available to plants. Bicarbonate-P also includes fulvic acid P, humic acid P and microbial P, which all must be mineralised before P can be absorbed by plants. Hydroxide-P, however, is non labile and is sparingly available to plants. 24 This fraction consists of P occluded by Fe oxides, stegnite P and P in fulvic and humic acids. HCl-P is also non labile and this fraction consists mainly of apatite mineral which becomes available as the soil becomes acidified. The final fraction is Residual-P, which consists partly of P occluded primarily by silicate minerals and partly of very resistant and non-extractable P trapped in mineral materials. Soil samples taken at the depths 0-20, 20-40, 40-60, 60-80 and 80-100 cm within an area of 10 m2 on five occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) were used. Three replicates were taken at each depth on each occasion. The samples were air-dried at 40◦C and then crushed and passed through a sieve of 2 mm. A scheme of fractionation is depicted in Figure 6. Thus, 1g of the sample of ≤2mm was suspended in 60 ml deionised water. A bag of resin (Cl- anion exchanger) was added and the sample shaken for 16 h (Stage 1). The resin bag was removed from the solution. The soil particles on the bag were carefully washed off with deionised water into the solution. The solution was centrifuged at 3500 rpm for 10 min. The liquid was then carefully decanted off and thrown away, leaving a ‘soil cake’. This ‘cake’ was used in the next fractionation stage. The bag of resin was extracted with 60 ml of 0.5 M HCl, shaken for 1 h and the solution was then used for P analysis (Resin-P). To the ‘cake’, 60 ml 0.5 M NaHCO3 at pH 8.5 was added (Stage 2). The solution was shaken for 16 h, then centrifuged at 3500 rpm for 10 min. The liquid was decanted off and saved for P analysis (Bicarbonate-P). To the remaining ‘cake’, 60 ml of 0.1 M NaOH at pH above 12 was added (Stage 3). The solution was shaken for 16 h, then centrifuged at 3500 rpm for 10 min. The liquid was decanted off and saved for P analysis (Hydroxide-P). To the remaining ‘cake’, 60 ml of 1 M HCl was added (Stage 4). The solution was shaken for 16 h, then centrifuged at 3500 rpm for 10 min. The liquid was decanted off and saved for P analysis (HCl-P). A separation into inorganic-P and organic-P of the fractions Bicarbonate-P and Hydroxide-P was conducted. Two samples from the solution saved for P analysis (Stages 2 and 3) were taken from each of the two fractions. One was used for measurement of Total-P (BicarbonateP and Hydroxide-P) and one for measurement of Inorganic-P (Bicarbonate-IP and HydroxideIP). Organic-P (Bicarbonate-OP and Hydroxide-OP) was then obtained by subtracting Inorganic-P from Total-P, as shown in Figure 6. To analyse Inorganic-P, the organic colloids were coagulated by adding 1 ml 0.9 M H2SO4 to 10 ml extractant. The solution was then centrifuged at 3500 rpm for 10 min and the liquid was decanted off and used for P analysis. To analyse Total-P, a sample of 5 ml solution was digested in a mixture of 2 ml of 97% H2SO4 and 1 ml of 25% H2O2 until clear. The digestate was used for P analysis. To obtain Total-P of the soil, a new sample from the dried, crushed and sieved soil consisting of 2 g of the fraction ≤ 2 mm was incinerated and the ash was dissolved in 10 ml of 1 M HCl and then analysed. 25 Stage 1 Stage 2 Resin-P 1g soil + HCO3- (resin) bag in H2O Shake Centrif. Stage 3 Stage 4 Bicarbonate-P Hydroxide-P Soil 0.5 M NaHCO3 Shake Centrifuge Soil 0.1 M NaOH Shake Centrifuge HCl-P Soil 1 M HCl Shake Centrifuge Stage 5 Residual-P Soil Digest (97% H2SO4 – 25% H2O2) Discard Solution Bag + 0.5 M HCl Shake 1 h Separation of P forms Separation of P forms P-analysis P-analysis in digestate Bag washed in 0.5 M HCl and preserved in 0.1 M HCl P-analysis Digest (97% H2SO4 – 25% H2O2) Remove organics with 0.9 M H2SO4 Digest (97% H2SO4 – 25% H2O2) Remove organics with 0.9 M H2SO4 P-analysis P-analysis Total-P Inorganic-P Total-P Inorganic-P Total-P- Inorganic-P = Organic-P Figure 6. A scheme for fractionating P, redrawn from Otabbong & Persson, 1994. The soil used was air-dried and passed through a sieve of ≤ 2 mm. The samples were shaken for 16 h and centrifuged at 3500 rpm. In this study, the extraction was ended at the HCl-stage. The Total-P was determined by fusion. Residual-P was obtained by subtracting Resin-P, Bicarbonate-P, Hydroxide-P and HCl-P from Total-P. 5.3.2. Phosphorus analysis To determine P from the different stages, the molybdate ascorbic acid procedure (Murphy & Riley, 1962) was used colorimetrically on the saved solutions. To enable solutions with high concentrations to be analysed, some had to be diluted before analysis. The principle of the method is as follows: 5 ml of the saved solution was transferred into a 25 ml bottle, 2 drops of methyl orange was added and the solution was titrated to a weak yellowish colour. Two ml of ascorbic molybdate were added and the solution was diluted to 25 ml with deionised water. The colour intensity was then measured at 880 nm on a colorimeter. The result was then compared with a standard curve and P was subsequently determined. 26 5.3.3. pH analysis A soil sample of 1 g was suspended in 10 ml deionised water and shaken for 30 min and pH was determined on a pH-meter at accuracy of ± 0.01 units. 5.3.4. Statistics The results were subjected to statistical analysis of variance and Pearson’s correlation, using the SAS Institute software (2000). Means for depth and seasons were separated at the Student’s t-test (p<0.05) and relationships among the fractions was based on Pearson’s linear correlation coefficients (r) at 95% probability. 27 6. Results and discussion 6.1 Phosphorus fractions and pH The results as mean values for the five sampling occasions of each P fraction and pH at different depths are depicted in Figures 7-12, with more information listed in the Appendices, Tables A1- A6. The three dominant fractions were Bicarbonate-P, Hydroxide-P and Residual-P, which together made up about 95-97% of Total-P (TP). As a general observation the upper layers (020, 20-40 cm) tended to have the highest amounts of P, which decreased with depth (40-60, 60-80, 80-100 cm). The fraction Resin-P ranged between 1.0 and 1.3% of TP and formed the smallest part of TP (Figure 7 and Table A2). In absolute values Resin-P ranged between 21 and 33 mg/kg (Figure 8 and Table A1) and tended to decrease down the profile whereas Resin-P as a percentage did not show such a trend. Bicarbonate-P ranged between 19 and 42% of TP (Figure 7 and Table A2) and between 295 and 1190 mg/kg (Figure 8 and Table A1). Bicarbonate-P showed the same trend as a percentage as it did in absolute values, with the highest values being recorded in the upper layers (0-20, 20-40 cm) whereafter the values decreased with depth (40-60, 60-80, 80-100 cm). Hydroxide-P ranged between 32 and 42% of TP (Figure 7 and Table A2) and in absolute values between 648 and 1201 mg/kg (Figure 8 and Table A1). Hydroxide-P showed the same trend in absolute values as Bicarbonate-P, with the highest values recorded in the upper layers (0-20, 20-40 cm) and a decreasing trend with depth (40-60, 60-80, 80-100 cm). However when expressed as a percentage, the opposite trend was observed. HCl-P also formed a small part of TP and ranged between 1.7 and 3.3% of TP (Figure 7 and Table A2). In absolute values, HCl-P ranged between 27 and 97 mg/kg (Figure 8 and Table A1). In general, HCl-P tended to decrease down the profile. Residual-P ranged between 22 and 37% of TP (Figure 7 and Table A2) or between 554 and 919 mg/kg (Figure 8 and Table A1). 28 P content of TP, % 45 a a 40 a 35 a ab b a a b 30 ab ab b 25 b b b 20 15 10 5 a bc a a ab a bc a c a 0 0-20 Resin-P 20-40 Bicarbonate-P 40-60 Hydroxide-P HCl-P 60-80 80-100 Depth (cm) Residual-P P content, mg/kg Figure 7. Distribution of phosphorus (P) content as a percentage of Total-P (TP) in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001). Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 1400 a 1200 a a a 1000 a ab 800 b 600 b ab b b b ab b 400 b 200 b a ab a ab b b c b c 0 0-20 Resin-P Bicarbonate-P 20-40 Hydroxide-P 40-60 HCl-P Residual-P 60-80 80-100 Depth (cm) Figure 8. Distribution of phosphorus (P) content in mg/kg in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001). Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 6.1.1. Bicarbonate Organic and Inorganic Phosphorus The distributions of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) are shown in Figure 9 and Tables A3 and A4. Bicarbonate-IP and Bicarbonate-OP both showed the same trend as Bicarbonate-P, with the highest values in the upper layers (0-20, 20-40 cm) and a decreasing trend for the other layers down the profile. Bicarbonate-IP was higher than Bicarbonate-OP in the upper layers (0-20, 20-40 cm) whereas Bicarbonate-OP was slightly higher than Bicarbonate-IP in the layers below (40-60, 60-80, 80-100 cm) (Figure 9). Bicarbonate-IP ranged between 141 and 744 mg/kg, whereas Bicarbonate-OP ranged between 155 and 516 mg/kg (Figure 9 and Table A3). Expressed as a percentage, Bicarbonate-IP ranged between 46 and 59% of Bicarbonate-P and 29 Bicarbonate OP and IP content, mg/kg Bicarbonate-OP ranged between 41 and 53% of Bicarbonate-P (Table A4). Bicarbonate-IP had the highest percentage, ranging between 55 and 59% of Bicarbonate-P in the upper layers (0-20, 20-40 cm) and decreasing to about 47% in the layers below (40-60, 60-80, 80-100 cm), whereas Bicarbonate-OP ranged between 41 and 45 % of Bicarbonate-P in the upper layers (0-20, 20-40 cm) and increased to about 53% in the layers below (40-60, 60-80, 80-100 cm) (Table A4). 800 a a 700 600 500 a a 400 b 300 b 200 b b b b 100 0 0-20 Bicarbonate-OP 20-40 Bicarbonate-IP 40-60 60-80 80-100 depth (cm) Figure 9. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) in mg/kg in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001). Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 6.1.2. Hydroxide Organic and Inorganic Phosphorus The distributions of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) are shown in mg/kg in Figure 10 and Tables A3 and A4. Hydroxide-OP accounted for the largest fraction of Hydroxide-P and ranged between 78 and 84% (Table A4). Hydroxide-OP ranged between 517 and 986 mg/kg, whereas HydroxideIP ranged between 125 and 216 mg/kg (Figure 10 and Table A3). In absolute values Hydroxide-OP was highest in the uppermost layers (0-20, 20-40 cm) and decreased down the profile (Figure 10) as did the general trend of Hydroxide-P (Figure 8), whereas Hydroxide-IP showed a slight decreasing trend down the profile. However as percentages, there were no differences for either Hydroxide-OP or Hydroxide-IP down the profile (Table A4). 30 Hydroxide OP and IP content, mg/kg 1100 1000 a 900 a 800 700 b 600 b b 500 400 300 a 200 a a 100 a a 0 0-20 Hydroxide-OP 20-40 Hydroxide-IP 40-60 60-80 80-100 Depth (cm ) Figure 10. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) in mg/kg in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001). Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 6.1.3. Total Organic and Inorganic Phosphorus As no mineral soil was observed in the studied soil profile, the assumption were made that Residual-P was organically bound P. Hence, Total Organic Phosphorus (Total-OP) was the sum of Bicarbonate-OP, Hydroxide-OP and Residual-P. Total Inorganic Phosphorus (TotalIP) was the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P. The distributions of Total-OP and Total-IP are shown in Figure 11 and Tables A5 and A6. Total-OP made up the biggest share of TP and ranged between 66 and 79% (Table A6). Total-OP ranged in absolute values between 1257 and 2421 mg/kg, whereas Total-IP ranged between 321 and 987 mg/kg (Figure 11 and Table A5). Total-OP and Total-IP showed the same trend with the highest values in the upper layers (0-20, 20-40 cm) and for the other layers (40-60, 60-80, 80-100 cm) a decreasing trend down the profile. 31 Total OP and IP content, mg/kg 3000 2500 a a 2000 b b 1500 b a 1000 a b 500 b b 0 0-20 Total-OP Total-IP 20-40 40-60 60-80 80-100 Depth (cm) Figure 11. Distribution of Total Organic Phosphorus (Total-OP) and Total Inorganic Phosphorus (Total-IP) in mg/kg in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001), where Total-OP is the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP, whereas Total-IP is the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. pH 6.1.4. pH The distribution of pH is shown in Figure 12 and Table A1. The pH ranged between 3.9 and 5.3, with its lowest value in the 40-60 cm layer and its maximum value at in the 80-100 cm layer. 6 5 ab a b c d 4 3 2 1 0 0-20 20-40 40-60 60-80 80-100 Depth (cm) Figure 12. pH in the soil profile, as mean values based on the results on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001). Mean values with similar letters are not statistically different at 95% probability. 32 6.2. Phosphorus fractions and pH at different depths and dates In addition to the results presented in Figures 7 -12, pH changes and P distribution in the soil profile for each date (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at each depth (0-20, 20-40, 40-60, 60-80 and 80-100 cm) are shown in Figures 13-21 and Figures A1-A13 and listed in Tables A7-A36. 6.2.1. Total Phosphorus The distribution of Total-P at different depths is shown for the five sampling occasions in mg/kg in Figure 13 and in Tables A7, A13, A19, A25 and A31. Total-P ranged between 1434 and 4319 mg/kg. As noted above, the upper layers (0-20, 20-40 cm) tended to have the highest values (2553-4319 mg/kg). In the layers below (40-60, 60-80, 80-100 cm) the amount of TP was about the same (1434-2286 mg/kg) down the profile and no change was observed over the season. However, in the upper layers (0-20, 20-40 cm) the values in September, October and November were higher (2983-4319 mg/kg) than those in April and June (25533202 mg/kg). The higher values in the autumn coincided with the end of the growing period (Figure 5). Although the temperature limit for the growing period (5oC air temperature, wwwmarkinfo.slu.se) was not exceeded, growth was slowing down and plants were decaying. During the winter the sampling site was inundated, causing anaerobic conditions and leaching could theoretically occur, which was indicated by the lower values in April. To ta l-P co n te n t, m g /kg 0 1000 2000 3000 4000 5000 D e p th (cm ) 0 -2 0 2001-04-15 2000-09-05 2001-06-05 2000-10-08 2 0 -4 0 4 0 -6 0 6 0 -8 0 2000-11-11 8 0 -1 0 0 Figure 13. Distribution of Total-P content in mg/kg in the soil profile on the five sampling occasions. 33 6.2.2. Resin-extractable Phosphorus The Resin-P values at different depths are shown for the five sampling occasions in absolute values in Figure 14 and in Tables A7, A13, A19, A25 and A31 and as a percentage of TP in Tables A8, A14, A20, A26 and A32 and Figure A1. Resin-P, which is biologically available and soluble, ranged between 16 and 46 mg/kg (Figure 14 and Tables A7, A13, A19, A25 and A31) and between 0.39 and 2.00% of TP (Tables A8, A14, A20, A26 and A32 and Figure A1). The amount of Resin-P varied in the upper part of the profile (0-20, 20-40 cm), ranging between 17 and 46 mg/kg, and showed a decreasing trend (16-36 mg/kg) with depth (40-60, 60-80, 80-100 cm). The highest values in mg/kg were observed in the upper two layers (0-20, 20-40 cm) in April and June (34-46 mg/kg) whereas the lowest value was observed in November (17-20 mg/kg). As a percentage of TP (Figure A1), an increasing trend with depth was observed, ranging between 0.53 and 1.70 % in the top layer (0-20 cm) and between 1.15 and 1.77 % in the bottom layer (80-100 cm). In the upper part of the profile (0-20, 20-40 cm), the values in April and June were higher (1.15-1.70 % of TP) than those in September, October and November (0.39-0.94 % of TP). R e sin -P co n te n t, m g /kg 0 10 20 30 40 50 D e p th (cm ) 0 -2 0 2001-04-15 2000-09-05 2001-06-05 2000-10-08 2 0 -4 0 4 0 -6 0 6 0 -8 0 2000-11-11 8 0 -1 0 0 Figure 14. Distribution of Resin-P content in mg/kg in the soil profile on five sampling occasions. 6.2.3. Bicarbonate-soluble Phosphorus Bicarbonate-P values at different depths are shown for the five sampling occasions in absolute values in Figure 15 and Tables A7, A13, A19, A25 and A31 and as a percentage of TP in Tables A8, A14, A20, A26 and A32 and Figure A2. Bicarbonate-P, which is readily available to plants, ranged between 289 and 1624 mg/kg (Figure 15 and Tables A7, A13, A19, A25 and A31) and as a percentage between 17 and 56% of TP (Tables A8, A14, A20, A26 and A32 and Figure A2). Bicarbonate-P showed a decreasing trend down the profile in both absolute 34 values and as a percentage of TP. However, the absolute values in November, April and June increased in the 20-40 cm layer and then decreased down the profile (Figure 15). As a percentage only, the values in April and June increased in the 20-40 cm layer (Figure A2). The highest values were observed in the upper two layers (0-20, 20-40 cm), ranging between 30-55% of TP (A8, A14) and between 819-1624 mg/kg (A7, A13). 0 400 B ica rb o n a te -P co n te n t, m g /kg 800 1200 1600 2000 D e p th (cm ) 0 -2 0 2001-04-15 2000-09-05 2001-06-05 2000-10-08 2 0 -4 0 4 0 -6 0 6 0 -8 0 2000-11-11 8 0 -1 0 0 Figure 15. Distribution of Bicarbonate-P content in mg/kg in the soil profile on five sampling occasions. 6.2.3.1. Bicarbonate-soluble Organic and Inorganic Phosphorus The distributions of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) are shown for the five sampling occasions in absolute values in Tables A9, A15, A21, A27 and A33 and as a percentage of Bicarbonate-P in Figure 16, Tables A10, A16, A22, A28 and A34 and Figures A6-A9. Bicarbonate-OP ranged between 21 and 64% of Bicarbonate-P. Bicarbonate-OP dominated the layers 40-60, 60-80 and 80-100 cm, ranging between 50 and 64% of Bicarbonate-P, with the exception of the values in October at 40-60 cm and April and June at 80-100 cm, which all were lower than 50%. The biggest change was in the top layer (0-20 cm) (Table A10), where Bicarbonate-OP was 21% in September, increased to about 60% in October and November and decreased again in April and June to around 40%. In the other layers the change between BicarbonateOP and Bicarbonate-IP was not so great (Figures A6-A9). 35 Bicarbonate OP and IP (% of Bicarbonate-P) 100 90 a c c b a b 3 4 b 80 70 60 50 40 30 20 10 c a b 0 1 Bicarbonate OP 2 Bicarbonate IP 5 Sampling occasions Figure 16. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) as a percentage of Bicarbonate-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at 0-20 cm depth. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 6.2.4. Hydroxide-soluble Phosphorus Hydroxide-P ranged between 521 and 1638 mg/kg (Figure 17 and Tables A7, A13, A19, A25 and A31) and as a percentage between 29 and 48% of TP (Tables A8, A14, A20, A26 and A32 and Figure A3). Hydroxide-P tended to decrease with depth. The highest values (7781638 mg/kg) were observed in the upper layers (0-20, 20-40 cm) and decreased to 872-521 mg/kg in the layers below (40-60, 60-80, 80-100 cm), where no change was observed over the season. It might be worth noting that the absolute values in April and June at 0-20 and 20-40 cm were lower (778-918 mg/kg) than those in September, October and November (876-1638 mg/kg). Furthermore, the absolute values increased in the upper layers (0-20, 20-40 cm) from September (876-1239 mg/kg) to November (1333-1638 mg/kg). As a percentage of TP, Hydroxide-P tended to increase with depth. In the top layer (0-20 cm) October and November tended to have the highest values (40-44% of TP), whereas the values in September, April and June were lower (29-32 % of TP). 36 Hydroxide-P content, mg/kg 0 300 600 900 1200 1500 1800 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 depth (cm) 2000-11-11 80-100 Figure 17. Distribution of Hydroxide-P content in mg/kg in the soil profile on five sampling occasions. 6.2.4.1. Hydroxide-soluble Organic and Inorganic Phosphorus The distributions of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) are shown for the five sampling occasions in absolute values in Tables A9, A15, A21, A27 and A33 and as a percentage of Hydroxide-P in Figure 18, Tables A10, A16, A22, A28 and A34 and Figures A10-A13. In absolute values Hydroxide-IP ranged between 22 and 388 mg/kg and Hydroxide-OP ranged between 3731002 mg/kg. Hydroxide-OP ranged between 56 and 97% of Hydroxide-P (Figure 18, Tables A10, A16, A22, A28 and A34 and Figures A10-A13) and hence dominated all layers. The largest variation was in the top layer (0-20 cm), with Hydroxide-OP ranging between 60-93% of Hydroxide-P over the seasons. 37 Hydroxide OP and IP (% of Hydroxide-P) 100 90 b ab b a b a ab a b a 80 70 60 50 40 30 20 10 0 1 Hydroxide OP 2 Hydroxide IP 3 4 5 Sampling occasions Figure 18. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) as a percentage of Hydroxide-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at 0-20 cm depth. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 6.2.5 Hydrochloric acid-soluble Phosphorus HCl-P ranged between 23 and 128 mg/kg (Figure 19 and Tables A7, A13, A 19, A25 and A31) and between 1.1 and 4.8% of TP (Figure A4 and Tables A8, A14, A 20, A26 and A32), and hence accounted for a small part of TP. For all five sampling occasions the same trend was observed both in absolute values and as a percentage of TP, with an increase from the upper layer (0-20 cm) (44-71 mg/kg and 1.10-2.15 % of TP) to the second layer (20-40 cm) (88-128 mg/kg and 2.04-4.84 % of TP) and then a decrease down the profile. It is worth noting that the absolute value in June for the 20-40 cm increased to 128 mg/kg, whereas the values from September, October, November and April ranged between 88 and 97 mg/kg (Figure 19 and Table A13). As a percentage, however, the trend with increased values in the 20-40 cm layer was not so distinct for October and November, whereas in September, April and June that trend was clear (Figure A4, Table A14). 38 HCl-P content, mg/kg 0 20 40 60 80 100 120 140 Depth (cm) 0-20 20-40 2001-04-15 2000-09-05 2001-06-05 2000-10-08 40-60 60-80 2000-11-11 80-100 Figure 19. Distribution of HCl-P content in mg/kg in the soil profile on five sampling occasions. 6.2.6. Residual Phosphorus The fraction Residual-P at different depths is shown for the five sampling occasions in mg/kg in Figure 20 and Tables A7, A13, A 19, A25 and A31 and as a percentage in Figure A5 and Tables A8, A14, A 20, A26 and A32. Residual-P ranged between 224 and 1537 mg/kg (Figure 20 and Tables A7, A13, A 19, A25 and A31) and as a percentage between 8 and 44% of TP (Figure A5 and Tables A8, A14, A 20, A26 and A32). The biggest change was observed in the 20-40 cm layer, where the absolute values in April and June decreased to the same value, 224 mg/kg, whereas the values in November increased to 1537 mg/kg, which was the highest value for this fraction (Table A13). The values in September and October increased only slightly at the same layer (20-40 cm). The percentage of TP (Figure A5) showed the same trend, as did the values in mg/kg in the top layers (0-20, 20-40 cm). In the layers below (40-60, 60-80, 80-100 cm), however, the values as a percentage slightly increased whereas the absolute values slightly decreased. 39 Residual-P content, mg/kg 0 400 800 1200 1600 2000 Depth (cm) 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 2000-11-11 80-100 Figure 20. Distribution of Residual-P content in mg/kg in the soil profile on five sampling occasions. 6.2.7. pH The pH at different depths is shown for the five sampling occasions in Figure 21 and Tables A7, A13, A19, A25 and A31. The pH ranged between 3.5 and 5.6. It tended to decrease from the upper layer (0-20 cm) down to the 40-60 cm layer and then increase again in the layers below. 40 pH 0 1 2 3 4 5 6 D e p th (cm ) 0 -2 0 20 -4 0 2000-09-05 2001-04-15 40 -6 0 2000-10-08 2001-06-05 60 -8 0 2000-11-11 8 0-1 0 0 Figure 21. Distribution of pH in the soil profile on five sampling occasions. 6.3 Correlations Correlations of P fractions are shown in Tables 6 and 7. Caution should be taken when interpreting correlations since the number of samples was not large (n=25). However, the results show some trends of relationship among the P fractions. Most of the correlations based on the absolute values were positive, whereas negative correlations were obtained when values were expressed as percentages. In the latter case it is worth noting the relationship between Residual-P and HCl-P, between Residual-P and Bicarbonate-P, between HCl-P and Hydroxide-P, and between Hydroxide-P and Bicarbonate-P, which were significant and negative, implying that either one increases at the expense of the other. Even if the correlations based on percentages were not significant between Resin-P and Bicarbonate-P, a negative correlation was noted that theoretically would mean that the fractions transformed into each other. Table 6. Correlations among phosphorus (P) fractions based on mean values as a % of TP on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001), where n =25 HCl-P Residual-P Resin-P Bicarbonate-P Hydroxide-P -0.40* 0.04 0.08 -0.57** Bicarbonate-P 0.56** -0.83*** -0.13 Resin-P 0.27 0.02 Residual- P -0.50** * p = 0.05; ** 0.05 > p ≥ 0.01; *** 0.01> p 41 Table 7. Correlation between phosphorus (P) fractions based on mean values in mg/kg on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) where n =25 HCl-P Residual-P Bicarbonate-IP Bicarbonate-OP Hydroxide-IP Hydroxide-OP Resin-P 0.45** -0.06 0.41** 0.36 -0.11 0.09 Hydroxide-OP 0.49** 0.42** 0.61*** 0.76*** 0.30 Hydroxide-IP 0.05 0.54*** 0.28 0.30 Bicarbonate-OP 0.79*** 0.18 0.64*** Bicarbonate-IP 0.66*** 0.39 Residual P 0.14 * p = 0.05; ** 0.05 > p ≥ 0.01; *** 0.01> p 6.4. General discussion We are aware that P may have been added to the sampling site, when for example the soil was inundated by the nutrient-rich stream Vinneå or via animal droppings from e.g. the huge flocks of geese that spend the winter in southern Sweden. P has most likely been added via decaying plants, but in this study only soil was examined. We are also aware that P may have been lost to the soil solution or through leaching, or via plant uptake. These types of features are important but were not accounted for in this study. We are also aware that the water level in the stream and the groundwater level are important features but we did not have the possibility to monitor them. Soil pH, moisture content, chemical relationships and temperature control the transformation of P in soils. Theoretically during the vegetative period when the soil is mostly aerobic, soluble P can be absorbed by plants and microbes or can be precipitated by compounds like Fe, Al and Mn. When inundation causes anaerobic conditions, however, plant and microbial activity decreases and P can be released from compounds of Fe, Al and Mn. During the winter when temperature is low biological activity ceases, leading to decreased biological transformation of P and no plant uptake. When soil pH is lower than 7.2, soluble P is adsorbed to clay minerals and Fe/Al-oxides and/or is precipitated as Fe/Al-P secondary minerals. P also competes with organic and inorganic compounds for bonding sites or can be adsorbed by organic compounds. Total-P content in this study was largest in the upper layers (0-20, 20-40 cm) and showed a variation over the seasons in those layers, whereas in the layers below (40-60, 60-80, 80-100 cm) no great variation was noted. Börling (2003) showed a similar trend with high amounts of P in the upper 40 cm of fertilized arable land which was not shown for non-fertilized arable land. In addition, the inundating stream in the present study contains high amounts of P, most likely originating from upstream arable land (Fristedt, 1999). These facts indicate that high amounts of P may have been incorporated into the soil over a long period of time, but the reason is not clear. Generally the upper 30 cm of a soil profile are characterised by high root density (Richardson & Marshall, 1986; Jackson et al., 1996) and thus high biological activity. The variation over the season in this study indicated a high biological activity in the upper 40 cm. The highest Total-P content in the upper 40 cm was noted in November, ranging between 3738 and 4319 mg/kg. This is at the end of the growing period, when plants have been decaying, which may have added P to the soil. According to Richardson & Marshall (1986), about 35% of aboveground P uptake by plants is returned to the ground surface via litter fall. 42 In April, however, the Total-P content in the upper 40 cm was at its lowest, ranging between 2646 and 3202 mg/kg. This sampling occasion was preceded by a period of high water levels and leaching may theoretically have occurred. Mahapatra & Patrick (1969) show that iron and aluminium phosphates increase during waterlogged conditions. They also show that the iron phosphate originates partly from the reductant soluble iron phosphate. In addition, Diaz, Anderson & Hanlon (1993) show that an increasing amount of total P is mineralised under flooded conditions and that flooding significantly increases the amount of Total P released into the drainage effluents. They also found that the leachate contains soluble inorganic and organic P and that the amount of leached organic P is greater under flooded conditions. When the sample in April was taken, the growing period was just starting (Figure 5) and had been preceded by an inundated and cool period. Theoretically, when the soil becomes more aerated and the temperature increases, microbial activity increases (Gross et al., 1995). Microbes promote the transformation of unavailable P to available P. An increased microbial activity would thereby release more P. This study indicates that the amount of soluble P is highest in spring and early summer. However, there were no samples taken of the soil solution, nor was plant material analysed. It is therefore hard to say how much soluble P there really was. One would expect a high plant uptake during the summer and chemical release during the anaerobic conditions in winter time. In this study the soluble pool (Resin-P) behaved differently in the profile over the seasons. For example most of the transformations seemed to occur in the 0-20 and 20-40 cm layers. Over the seasons, the soluble pool was largest in April and June and lowest in November. However, theoretically, an unknown portion of this fraction should be in the soil solution, but no such study was conducted. The readily available P pool (Bicarbonate-P) also behaved differently in the profile over the seasons. In this pool too, most of the transformations seemed to occur in the upper layers (020, 20-40 cm). This pool seemed to have the opposite trend as a percentage of TP compared with the resistant P pool (Residual-P), in that Bicarbonate-P decreased down the profile (Figure A2) whereas Residual-P increased down the profile (Figure A5). In April and June there was a clear trend in the 20-40 cm layer where Bicarbonate-P increased whereas Residual-P decreased. This, together with the significant correlation based on percentage of TP (Table 6), indicates that Residual-P transforms into Bicarbonate-P and vice versa. There was also a significant negative correlation as a percentage of TP between Bicarbonate-P and the sparingly plant available Hydroxide-P, which together with Figure 7 indicate that Bicarbonate-P transforms into Hydroxide-P. The non labile pool HCl-P had significant negative correlations as a percentage of TP (Table 6) with the also sparingly plant available Hydroxide-P and Residual-P, which indicates that HCl-P increases when Hydroxide-P or Residual-P decreases or vice versa. Figures A5 and A4 also indicate this trend where HCl-P decreases down the profile whereas Residual-P increases down the profile. Hydroxide-P also shows an increasing trend down the profile (Figure A3) but is not as clear as the trend shown for Residual-P. This study indicates that the P forms transform into each other and that most transformations occur in the upper 40 cm of the profile. The total P content is lower after the winter when the soil has been inundated, indicating loss of P, most likely through leaching. Most transformations seem to occur in spring and early summer, although since the loss or gain of P 43 via for example the inundating water and groundwater was not monitored, it is hard to draw any accurate conclusions on seasonal influences. 7. Conclusions P was mainly organically bound (66-79%) The upper 40 cm of the soil profile contained the largest amount of P (2553-4319 mg/kg) The Total-P content decreased during the winter when the soil was inundated Bicarbonate-extractable P transformed into the resistant P pool and vice versa Bicarbonate-extractable P transformed into Hydroxide-extractable P and vice versa The resistant P pool transformed into HCl-extractable P and vice versa The HCl-extractable P transformed into Hydroxide-extractable P and vice versa The largest transformations occurred in spring and early summer 7.1. Concluding remarks Riparian wetlands are complex systems, and are influenced by the adjacent water and also by biological life in the form of plants and animals. It was therefore hard to monitor the real gain or loss of P. To understand the dynamics of P in such wetland, it is important to examine crucial features such as loss or gain via the inundating stream or via the groundwater. The uptake via plants is another interesting feature worth investigating. 44 8. Acknowledgements This study was conducted within the EU project Prowater ‘Program for Prevention of Diffuse Pollution with Phosphorus from Degraded and Re-wetted Peat Soils’ (PROWATER-EVICICT-1999-00036) financed by European Union. The Swedish University of Agricultural Sciences (SLU) supported the MSc studies. I would like to thank my main supervisor Professor Erasmus Otabbong for introducing me to the interesting subject of soil science and soil phosphorus. I especially want to thank my second supervisor Dr. Elve Lode, for her enormous support and for always being there for me. I also want to thank Per Edenhamn, Gerd Johansson and Brita Sjögren who made it possible for me to finish this report. To Ragnar Persson, who helped me with all my computer problems. Furthermore I would like to thank the owner of the sampling site and the friendly neighbours in the site area. Thanks to the people at the Department of MNA at the University of Kristianstad and to Karin Magntorn, Kristianstad vattenrike. I also would like to thank Dr. Mary McAfee who edited my English. Finally I would like to thank my family and friends who have supported me, and especially Emil, who has been there for me unconditionally. 45 9. References Amador, J.A., Richany, G. H. & Jones, R.D. 1992. Factors Affecting Phosphate Uptake by Peat Soils Florida Everglades. Soil Sci. vol. 153, no.6, 463-470 Barber, S. A. 1995. Soil Nutrient Bioavailability. A mechanistic approach, 2nd ed., 201-211. New York & Toronto: John Wiley & sons, Inc. Bloom, P.R. 1981. Phosphorus Adsorption by an Aluminium-Peat Complex. Soil Sci. S. Am. J. vol 45, 267-272. Börling, K. 2003. Phosphorus Sorption, Accumulation and leaching. Effects of long term inorganic fertilization of cultivated soils. (Doctoral Thesis. Swedish University of Agricultural Sciences. Agraria 428). Uppsala Sweden. Cronert, H. 1996. Våtmarksområdet utmed nedre Helgeån, från Torsebro till havet, 3 uppl. Länsstyrelsen i Kristianstad Län. Kristianstad. Diaz, O.A. Anderson, D.L. & Hanlon, E.A. 1993. Phosphorus Mineralization from Histosols of the Everglades Agricultural Area. Soil Sci. vol. 156, no. 3, 178-185. Donahue, R.L., Miller, R.W. & Shickluna, J.C. 1983. Soils. An introduction to soils and plant growth, 5th ed. 126-134. New Yersey: Prentice-Hall, Inc Fristedt, A. 1999. Vinneå. Inventering och åtgärdsförslag. Miljöskyddsprogrammet Rapport 1/99. Miljökontoret, Hässleholms kommun. Hässleholm. Gross, T., Faull, J., Ketteridge, S. & Springham, D. 1995. Introductory Microbiology, 51. London: Chapman & Hall. Havlin, J.L., Beaton, J.D., Tisdale, S.L. & Nelson, W.L. 1999. Soil Fertility and Fertilizers. An Introduction to Nutrient Management, 6thed. 154-195. New Jersey: Prentice-Hall Inc. Hedley, M.J., Stewart, J.W.B. & Chauhan, B.S. 1982. Change in inorganic soil phosphorus fractions induced by cultivation practices and laboratory incubations. Soil Sci. Am. J. vol 46, 970-976. Horne, A. J. & Goldman, C.R. 1994. Limnology. 2nd ed. 152-171. Singapore: McGraw-Hill Inc. Hughes, J.M.R. & Heathwaite, A.L. 1995. Introduction. In Hydrology and Hhydrochemistry of British Wetlands. (ed. J.M.R., Hughes & A.L., Heathwaite). Chichester: John Wiley & sons, Inc. Jackson, R.B., Canadell, J., Ehleringer, J.R., Monney, H.A., Sala, O.E., Schulze, E.D. 1996. A global analysis of root distributions for terrestrial biomes. Oceologia 108:389-411. Lönngren, G. 1995. 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Mitchell, R.L., Caldwell, B.E., Larson, W.E., 1980. Foreword. In The Role of Phosphorus in Agriculture. Wisconsin: American Society of Agronomy, Inc. Crop Science Society of America, Inc. Soil Science Society of America, Inc. Madison, Wisconsin USA Murphy, J., Riley, JP., 1962. A modified single solution method for the determination of phosphate in neutral waters. Anal Chim Acta 27, 31-36. Narurvårdsverket & Statistiska centralbyrån (SCB), 2000. Naturmiljön i siffror, 6 ed. Stockholm. Nilsson, C. 1999. Rivers and Streams (eds. E. Sjögren, H. Rydin, P. Snoeijs & M. Djekmann) Acta Phytogeorgr. Suec. 84.135-148. TK-tryck:Uppsala Otabbong, E & Fristedt, A. 2005. Phosphorus status, forms, distribution and seasonal variations in a flooded Histosol plain – A case of Kristianstad wetland, Southern Sweden. Special Issue of International Journal of Environmental Pollution. Submitted. Otabbong, E., Persson, J., 1994. Relative Agronomic Merit of Fused Calcium Phosphate III. Forms of Phosphorus in Soils Repeatedly Cropped in Pot Experiments. Acta Agric. Scand. Sect. B, Soil and Plant Sci. 44, 2-11. Denmark. Persson, J. 2003. Nitrogen losses and N management: possible improvements in agriculture: short term and long term soil biological processes with special regard to nitrogen. Report 207. Swedish University of Agricultural Sciences, Dept, of Soil sciences, Division of Soil Fertility. Raven, P.H., Evert, R.F., Eichhorn, S.E., 1999. Biology of Plants, 6th ed. 308, 589-597. New York: R.R. Donnelley. 47 Rekolainen, S., Ekholm, P., Ulén B. & Gustafson, A. 1997. Phosphorus losses from agriculture to surface waters in the Nordic countries. In Phosphorus loss from soil to water (ed. H., Tunney, O.T., Carton, P.C., Brookes & A.E., Johnston), 77-93. Guildfrod and Kong´s Lynn: Biddles Ltd. Richardson, J.C. & Marshall, E.P. 1986. Processes controlling movement, storage, and export of phosphorus in a fen peatland. Ecologival Monographs, 54(4), 279-302. Shen, C.Y. & Morgan, F.W. 1973. Hydrolysis of Phosphorus Compounds. In Environmental Phosphorus Handbook (ed. E. J., Griffith, A., Beeton, J.M., Spencer & D.T., Mitchell), 241264. New York: John Wiley & sons, Inc. Sjörs, H. 1999. The background. Geology, Climate and Zonation. (eds. E. Sjögren, H. Rydin, P. Snoeijs & M. Djekmann) Acta Phytogeorgr. Suec. 84:5-14. TK-tryck:Uppsala Stevenson, F.J. 1986. The Phosphorus cycle. In Cycles of soi: Carbon, Nitrogen,Phosphorus, Sulphur,Mmicronutrients. 231-284. New York: John Wiley & sons, Inc. Troedsson, T. & Wiberg, M. 1986. Sveriges Jordmåner. (Swedish Soil Map). Swedish University of Agricultural Sciences, Department of Forest Soils. Distributor: The Royal Swedish Academy of Agriculture and Forestry. P.O. Box 6806, 113 86 Stockholm. van Wazer, J. R. 1973. The Compounds of Phosphorus. In Environmental phosphorus handbook (ed. E. J., Griffith, A., Beeton, J.M., Spencer & D.T., Mitchell), 169-178. New York: John Wiley & sons, Inc. Wheeler, B.D. 1999. Water and plants in freshwater wetlands, ECO-Hydrology; Plants and water in terrestrial and aquatic environmenst. (ed. A.J., Baird & R.L., Wilby), 127-180. London & New York: Routledge Websites http://www.ramsar.org/key_conv_e.htm (20030909) http://www-markinfo.slu.se/sve/klimat/vegper.html (200030915) http://www.weather.vattenriket.kristianstad.se/cgi-win/vader.exe (200040928) Maps Figure A14: Lantmäteriverket, 1998, GSD-Digitalt ortofoto Dnr. 507-98-3015 Figure 4: Lantmäteriverket, ur GSD Röda kartan Dnr. 507-98-4720 Personal communication Erasmus Otabbong, Supervisor (2004) Karin Magntorn, Kristianstad Vattenrike, Kristianstad Kommun (08 12 2004) Barry Broman, SMHI (08 12 2004) 48 10. Appendices Appendix 1. Tables A1-A36: Raw data Table A1. pH and Phosphorus (P) fractions in mg/kg as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths Depth (cm) Total-P (mg/kg) pH Resin-P (mg/kg) Bicarbonate -P (mg/kg) Hydroxide- P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 5,1 ab 3408 a 33 a 1192 a 1201 a 62 b 919 a 0-20 4,8 b 3144 a 30 ab 1259 a 1004 a 97 a 754 ab 20-40 3,9 d 2012 b 27 ab 514 b 731 b 53 b 695 ab 40-60 4,4 c 1760 b 22 b 418 b 727 b 39 c 554 b 60-80 5,3 a 1577 b 21 b 295 b 648 b 27 c 585 ab 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. Table A2. Phosphorus (P) fractions in percentage of Total-P (TP) as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths Depth (cm) Resin-P % of TP Bicarbonate- P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 1,01 a 34,58 a 34,98 b 1,85 bc 27,58 ab 0-20 1,03 a 41,51 a 31,85 b 3,25 a 22,36 b 20-40 1,34 a 25,67 b 36,26 ab 2,65 ab 34,08 a 40-60 1,28 a 23,85 b 41,28 a 2,22 bc 31,37 ab 60-80 1,34 a 18,84 b 41,33 a 1,74 c 36,75 a 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. Table A3. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths Depth (cm) Bicarbonat-IP (mg/kg) Bicarbonat-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 677 a 516 a 216 a 986 a 0-20 744 a 515 a 176 a 828 a 20-40 240 b 274 b 125 a 606 b 40-60 195 b 223 b 160 a 567 b 60-80 141 b 155 b 132 a 517 b 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. Table A4. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and HydroxideP respectively as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths Depth (cm) Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide-OP % of Hydroxide-P 55,81 ab 44,19 ab 18,23 a 81,77 a 0-20 59,08 a 40,92 b 15,83 a 84,17 a 20-40 46,77 b 53,23 a 17,68 a 82,33 a 40-60 46,76 b 53,24 a 21,70 a 78,30 a 60-80 47,48 b 52,53 a 20,23 a 79,77 a 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. 49 Table A5. Distribution of Total Organic Phosphorus (Total-OP) and Total Inorganic Phosphorus (Total-IP) and Extractable Phosphorus (Extractable-P) in mg/kg as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, BicarbonateIP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Depth (cm) Extractable-P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 2489 a 2421 a 987 a 0-20 2390 a 2097 a 1047 a 20-40 1325 b 1575 b 445 b 40-60 1206 b 1343 b 417 b 60-80 992 b 1257 b 321 b 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. Table A6. Distribution of Total Inorganic (Total-IP) and Total Organic (Total-OP) Phosphorus and Extractable Phosphorus (Extractable-P) in percentage of Total-P (TP) as mean values on five sampling occasions (5th September 2000, 8th October 2000, 11th November 2000, 15th April 2001 and 5th June 2001) at different depths where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Depth (cm) Extractable-P % of TP Total-OP % of TP Total-IP % of TP 72,42 ab 71,18 bc 28,82 ab 0-20 77,66 a 66,15 c 33,85 a 20-40 65,92 b 77,73 ab 22,27 bc 40-60 68,64 ab 76,42 ab 23,58 bc 60-80 63,26 b 79,77 ab 20,23 c 80-100 Mean values with similar letters within the same fraction are not statistically different with 95% probability. Table A7. pH and Phosphorus (P) fractions in mg/kg on five sampling occasions at the depth of 0-20 cm Date pH Total-P (mg/kg) Resin-P (mg/kg) Bicarbonate-P (mg/kg) Hydroxide-P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 05-sep-00 5,3 a 3938 a 33 c 1624 a 1239 c 44 c 998 ab 08-okt-00 5,2 ab 3474 c 27 d 1300 b 1400 b 71 a 675 d 11-nov-00 4,8 c 3738 b 20 e 1206 b 1638 a 70 a 804 c 15-apr-01 5,0 bc 2688 e 46 a 819 d 865 d 55 b 904 bc 05-jun-01 5,3 a 3202 d 37 b 1058 c 918 d 69 a 1120 a Values with similar letters within the same fraction are not statistically different with 95% probability. Table A8. Phosphorus (P) fractions in percentage of Total-P (TP) on five sampling occasions at the depth of 0-20 cm Date Resin-P % of TP Bicarbonate-P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 05-sep-00 0,85 c 41,23 a 31,47 c 1,10 c 25,35 b 08-okt-00 0,78 c 37,42 b 40,30 b 2,04 a 19,45 c 11-nov-00 0,53 d 32,27 cd 43,81 a 1,88 b 21,51 c 15-apr-01 1,70 a 30,46 d 32,17 c 2,03 ab 33,65 a 05-jun-01 1,15 b 33,04 c 28,66 d 2,15 a 35 a Values with similar letters within the same fraction are not statistically different with 95% probability. 50 Table A9. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg on five sampling occasions at the depth of 0-20cm Date Bicarbonate-IP (mg/kg) Bicarbonate-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 05-sep-00 1272 a 353 b 239 a 1000 bc 08-okt-00 550 c 751 a 362 a 1038 b 11-nov-00 491 d 716 a 190 ab 1448 a 15-apr-01 490 d 329 b 349 a 516 d 05-jun-01 629 b 430 b 61 b 857 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A10. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and Hydroxide-P respectively as mean values on five sampling occasions at the depth of 0-20 cm Date Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide OP % of Hydroxide-P 05-sep-00 78,41 a 21,59 c 19,29 b 80,71 a 08-okt-00 42,30 c 57,70 a 25,88 ab 74,12 ab 11-nov-00 40,67 c 59,33 a 11,60 b 88,40 a 15-apr-01 59,80 b 40,20 b 40,25 a 59,75 b 05-jun-01 59,45 b 40,55 b 6,65 b 93,36 a Values with similar letters within the same fraction are not statistically different with 95% probability. Table A11. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic (TotalOP) Phosphorus and Extractable Phosphorus (Extractable-P) in mg/kg on five sampling occasions at the depth of 0-20 cm, where Total-OP was the sum of Residual-P, BicarbonateOP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable P was Total-P minus Residual-P Date Extractable-P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 05-sep-00 2940 a 2351 b 1587 a 08-okt-00 2798 a 2464 b 1010 b 11-nov-00 2934 a 2967 a 771 c 15-apr-01 1783 c 1749 c 939 bc 05-jun-01 2081 b 2406 b 795 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A12. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic (TotalOP) Phosphorus and Extractable-Phosphorus (Extractable –P) in percentage of Total-P (TP) on five sampling occasions at the depth of 0-20 cm, where Total-OP was the sum of ResidualP, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P % of TP Total-OP % of TP Total-IP % of TP 05-sep-00 74,65 b 59,67d 40,33 a 08-okt-00 80,55 a 70,93 bc 29,07 bc 11-nov-00 78,49 a 79,38 a 20,62 d 15-apr-01 66,35 c 65,07 cd 34,93 ab 05-jun-01 65,00 c 75,16 ab 24,84 cd Values with similar letters within the same fraction are not statistically different with 95% probability. 51 Table A13. pH and Phosphorus (P) fractions in mg/kg on five sampling occasions at the depth of 20-40 cm Date pH Total-P (mg/kg) Resin-P (mg/kg) Bicarbonate-P (mg/kg) Hydroxid-P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 05-sep-00 4,5 c 2983 c 25 d 944 c 876 c 96 b 1042 b 08-okt-00 4,8 a 3254 b 31 c 1088 b 1233 b 88 c 816 b 11-nov-00 5,3 a 4319 a 17 e 1345 a 1333 a 88 c 1537 a 15-apr-01 4,9 b 2553 d 34 b 1406 a 792 d 97 b 224 c 05-jun-01 4,8 b 2646 d 44 a 1474 a 778 d 128 a 224 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A14. Phosphorus (P) fractions in percentage of Total-P (TP) on five sampling occasions at the depth of 20-40 cm Date Resin-P % of TP Bicarbonate-P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 05-sep-00 0,84 d 31,74 b 29,42 b 3,21 c 34,79 a 08-okt-00 0,94 c 33,42 b 37,89 a 2,68 d 25,06 b 11-nov-00 0,39 e 31,13 b 30,86 b 2,04 e 35,58 a 15-apr-01 1,33 b 55,06 a 31,04 b 3,79 b 8,77 c 05-jun-01 1,65 a 55,67 a 29,41 b 4,84 a 8,43 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A15. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg on five sampling occasions at the depth of 20-40 cm Date Bicarbonate-IP (mg/kg) Bicarbonate-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 05-sep-00 599 d 345 d 134 c 743 c 08-okt-00 550 e 538 b 232 b 1002 a 11-nov-00 891 b 454 bc 388 a 946 b 15-apr-01 974 a 432 cd 83 d 710 d 05-jun-01 690 c 784 a 52 e 727 cd Values with similar letters within the same fraction are not statistically different with 95% probability. Table A16. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and HydroxideP respectively as mean values on five sampling occasions at the depth of 20-40 cm Date Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide-OP % of Hydroxide-P 05-sep-00 63,58 b 36,42 b 15,24 c 84,76 c 08-okt-00 50,53 c 49,47 a 18,78 b 81,22 d 11-nov-00 66,31 ab 33,69 bc 29,07 a 70,93 e 15-apr-01 69,36 ab 30,64 c 10,47 d 89,53 b 05-jun-01 46,79 c 53,21 a 6,62 e 93,38 a Values with similar letters within the same fraction are not statistically different with 95% probability. 52 Table A17. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in mg/kg on five sampling occasions at the depth of 20-40 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, BicarbonateIP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 05-sep-00 1940 c 2129 c 853 d 08-okt-00 2438 b 2356 b 899 c 11-nov-00 2782 a 2936 a 1383 a 15-apr-01 2329 b 1365 e 1188 b 05-jun-01 2424 b 1735 d 913 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A18. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in percentage of Total-P (TP) on five sampling occasions at the depth of 20-40 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P % of TP Total-OP % of TP Total-IP % of TP 05-sep-00 65,21 c 71,35 a 28,66 c 08-okt-00 74,94 b 72,37 a 27,63 c 11-nov-00 64,42 c 67,97 b 32,03 b 15-apr-01 91,23 a 53,47c 46,53 a 05-jun-01 91,57 a 65,51 b 34,49 b Values with similar letters within the same fraction are not statistically different with 95% probability. Table A19. pH and Phosphorus (P) fractions in mg/kg on five sampling occasions at the depth of 40-60 cm Date pH Total-P (mg/kg) Resin-P (mg/kg) Bicarbonate-P (mg/kg) Hydroxid-P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 05-sep-00 3,5 b 2033 b 26 ab 548 b 732 b 45 b 682 c 08-okt-00 4,0 a 2212 a 29 ab 461 c 872 a 54 a 797 b 11-nov-00 4,0 a 1825 c 22 b 607 a 675 bc 58 a 464 e 15-apr-01 4,0 a 2286 a 30 ab 558 b 710 b 53 a 936 a 05-jun-01 4,2 a 1779 c 36 a 427 d 637 c 56 a 623 d Values with similar letters within the same fraction are not statistically different with 95% probability. Table A20. Phosphorus (P) fractions in percentage of Total-P (TP) on five sampling occasions at the depth of 40-60 cm Date Resin-P % of TP Bicarbonate-P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 05-sep-00 1,29 b 26,95 b 36,00 b 2,19 c 33,58 c 08-okt-00 1,32 b 20,84 d 39,40 a 2,43 b 36,01 b 11-nov-00 1,22 b 33,23 a 36,96 b 3,17 a 25,42 d 15-apr-01 1,30 b 24,39 c 31,05 c 2,33 bc 40,93 a 05-jun-01 2,00 a 23,98 c 35,82 b 3,16 a 35,04 b Values with similar letters within the same fraction are not statistically different with 95% probability. 53 Table A21. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg on five sampling occasions at the depth of 40-60 cm Date Bicarbonate-IP (mg/kg) Bicarbonate-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 05-sep-00 263 a 285 b 159 a 574 b 08-okt-00 243 b 219 c 62 c 810 a 11-nov-00 271 a 336 a 131 b 544 bc 15-apr-01 239 b 319 a 135 b 575 b 05-jun-01 195 c 232 c 148 a 489 c Values with similar letters within the same fraction are not statistically different with 95% probability Table A22. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and HydroxideP respectively on five sampling occasions at the depth of 40-60 cm Date Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide-OP % of Hydroxide-P 05-sep-00 47,95 b 52,05 c 21,68 ab 78,32 cd 08-okt-00 52,61 a 47,39 d 7,11 d 92,89 a 11-nov-00 44,60 cd 55,40 ab 19,35 bc 80,65 bc 15-apr-01 42,90 d 57,10 ab 19,03 c 80,97 b 05-jun-01 45,59 c 54,41 b 23,25 a 76,75 d Values with similar letters within the same fraction are not statistically different with 95% probability. Table A23. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in mg/kg on five sampling occasions at the depth of 40-60 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, BicarbonateIP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 05-sep-00 1350 a 1541 b 492 a 08-okt-00 1416 a 1825 a 388 d 11-nov-00 1361 a 1344 c 482 ab 15-apr-01 1350 a 1829 a 457 bc 05-jun-01 1155 b 1344 c 434 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A24. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) Extractable Phosphorus (Extractable-P) in percentage of Total-P (TP) on five sampling occasions at the depth of 40-60 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P % of TP Total-OP % of TP Total-IP % of TP 05-sep-00 66,42 b 75,80 c 24,20 b 08-okt-00 63,99 c 82,48 a 17,52 d 11-nov-00 74,58 a 73,64 d 26,36 a 15-apr-01 59,07 d 80,00 b 20,00 c 05-jun-01 64,96 c 75,59 c 24,41 b Values with similar letters within the same fraction are not statistically different with 95% probability. 54 Table A25. pH and Phosphorus (P) fractions in mg/kg on five sampling occasions at the depth of 60-80 cm Date pH Total-P (mg/kg) Resin-P (mg/kg) Bicarbonate-P (mg/kg) Hydroxid-P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 05-sep-00 4,4 ab 1776 bc 21 cd 449 b 700 d 35 b 572 b 08-okt-00 4,7 ab 1718 c 23 bc 382 d 826 a 32 b 456 c 11-nov-00 4,3 b 1843 b 24 b 480 a 784 b 31 b 524 bc 15-apr-01 4,8 a 1968 a 19 d 386 cd 754 c 50 a 760 a 05-jun-01 4,6 ab 1551 d 27 a 399 c 591 e 54 a 481 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A26. Phosphorus (P) fractions in percentage of Total-P (TP) on five sampling occasions at the depth of 60-80 cm Date Resin-P % of TP Bicarbonate-P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 05-sep-00 1,17 b 25,26 a 39,40 c 1,98 c 32,2 b 08-okt-00 1,31 b 22,21 b 48,10 a 1,84 c 26,53 d 11-nov-00 1,31 b 26,03 a 42,56 b 1,68 c 28,43 cd 15-apr-01 0,94 c 19,60 c 38,30 c 2,55 b 38,61 a 05-jun-01 1,73 a 25,69 a 38,07 c 3,47 a 31,03 bc Values with similar letters within the same fraction are not statistically different with 95% probability. Table A27. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg on five sampling occasions at the depth of 60-80 cm Date Bicarbonate-IP (mg/kg) Bicarbonate-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 05-sep-00 172 b 277 a 129 c 571 b 08-okt-00 180 b 202 c 136 c 691 a 11-nov-00 238 a 242 b 188 b 570 b 15-apr-01 180 b 206 c 234 a 520 c 05-jun-01 186 b 213 c 59 d 532 c Values with similar letters within the same fraction are not statistically different with 95% probability Table A28. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and HydroxideP on five sampling occasions at the depth of 60-80 cm Date Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide-OP % of Hydroxide-P 05-sep-00 38,27 b 61,73 a 18,45 c 81,56 b 08-okt-00 47,18 a 52,82 b 16,40 c 83,60 b 11-nov-00 49,53 a 50,47 b 23,92 b 76,08 c 15-apr-01 46,70 a 53,30 b 31,05 a 68,95 d 05-jun-01 46,67 a 53,33 b 9,91 d 90,09 a Values with similar letters within the same fraction are not statistically different with 95% probability. 55 Table A29. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in mg/kg on five sampling occasions at the depth of 60-80 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, BicarbonateIP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable- P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 05-sep-00 1204 c 1419 ab 356 b 08-okt-00 1362 b 1348 b 370 b 11-nov-00 1319 a 1362 b 480 a 15-apr-01 1208 c 1485 a 483 a 05-jun-01 1070 d 1226 c 325 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A30. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in percentage of TotalP (TP) on five sampling occasions at the depth of 60-80 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P % of TP Total-OP % of TP Total-IP % of TP 05-sep-00 67,80 c 79,93 a 20,07 b 08-okt-00 73,47 a 78,47a 21,53 b 11-nov-00 71,58 ab 73,94 b 26,06 a 15-apr-01 61,39 d 75,47 b 24,53 a 05-jun-01 68,97 bc 79,03 a 20,97 b Values with similar letters within the same fraction are not statistically different with 95% probability. Table A31. pH and Phosphorus (P) fractions in mg/kg on five sampling occasions at the depth of 80-100 cm Date pH Total-P (mg/kg) Resin-P (mg/kg) Bicarbonate-P (mg/kg) Hydroxid-P (mg/kg) HCl-P (mg/kg) Residual-P (mg/kg) 05-sep-00 5,6 a 1826 a 26 a 305 a 682 b 37 a 777 a 08-okt-00 5,5 a 1559 b 28 a 306 a 737 a 25 b 464 bc 11-nov-00 5,0 b 1434 c 16 c 326 a 669 b 34 a 389 c 15-apr-01 5,5 a 1520 b 18 bc 289 a 521 d 25 b 668 a 05-jun-01 5,0 b 1510 b 21 b 304 a 641 c 23 b 520 b Values with similar letters within the same fraction are not statistically different with 95% probability. Table A32. Phosphorus (P) fractions in percentage of Total-P (TP) on five sampling occasions at the depth of 80-100 cm Date Resin-P % of TP Bicarbonate-P % of TP Hydroxide-P % of TP HCl-P % of TP Residual-P % of TP 05-sep-00 1,41 bc 16,69 b 37,3 c 2,03 ab 42,54 a 08-okt-00 1,77 a 19,60 ab 47,26 a 1,62 b 29,75 b 11-nov-00 1,15 c 22,70 a 46,62 a 2,40 a 27,14 b 15-apr-01 1,16 bc 19,01 ab 34,24 d 1,65 b 43,94 a 05-jun-01 1,42 b 20,10 ab 42,46 b 1,58 b 34,44 b Values with similar letters within the same fraction are not statistically different with 95% probability. 56 Table A33. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in mg/kg on five sampling occasions at the depth of 80-100 cm Date Bicarbonate-IP (mg/kg) Bicarbonat-OP (mg/kg) Hydroxide-IP (mg/kg) Hydroxide-OP (mg/kg) 05-sep-00 151 b 154 ab 190 a 492 d 08-okt-00 140 b 166 ab 206 a 531 c 11-nov-00 114 c 212 a 104 c 565 b 15-apr-01 146 b 144 ab 148 b 373 e 05-jun-01 168 a 136 b 22 d 619 a Values with similar letters within the same fraction are not statistically different with 95% probability. Table A34. Distribution of Inorganic Phosphorus (IP) and Organic Phosphorus (OP) within the fractions Bicarbonate-P and Hydroxide-P in percentage of Bicarbonate-P and HydroxideP respectively on five sampling occasions at the depth of 80-100 cm Date Bicarbonate-IP % of Bicarbonate-P Bicarbonate-OP % of Bicarbonate-P Hydroxide-IP % of Hydroxide-P Hydroxide-OP % of Hydroxide-P 05-sep-00 49,46 ab 50,54 bc 27,88 a 72,12 c 08-okt-00 45,84 b 54,17 b 27,97a 72,03 c 11-nov-00 35,41 c 64,59 a 15,48 b 84,52 b 15-apr-01 50,35 ab 49,65 bc 28,45 a 71,55 c 05-jun-01 55,34 a 44,66 c 3,43 c 96,57 a Values with similar letters within the same fraction are not statistically different with 95% probability. Table A35. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in mg/kg on five sampling occasions at the depth of 80-100 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, BicarbonateIP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P (mg/kg) Total-OP (mg/kg) Total-IP (mg/kg) 05-sep-00 1049 ab 1423 a 403 a 08-okt-00 1095 a 1160 c 399 a 11-nov-00 1045 ab 1166 c 268 c 15-apr-01 852 c 1184 c 336 b 05-jun-01 990 b 1275 b 235 c Values with similar letters within the same fraction are not statistically different with 95% probability. Table A36. Distribution of Total Inorganic Phosphorus (Total-IP) and Total Organic Phosphorus (Total-OP) and Extractable Phosphorus (Extractable-P) in percentage of TotalP (TP) on five sampling occasions at the depth of 80-100 cm, where Total-OP was the sum of Residual-P, Bicarbonate-OP and Hydroxide-OP whereas Total-IP were the sum of Resin-P, Bicarbonate-IP, Hydroxide-IP and HCl-P and were Extractable-P was Total-P minus Residual-P Date Extractable-P % of TP Total-OP % of TP Total-IP % of TP 05-sep-00 57,46 b 77,91 c 22,09 b 08-okt-00 70,25 a 74,41 d 25,59 a 11-nov-00 72,86 a 81,32 b 18,68 c 15-apr-01 56,06 b 77,89 c 22,15 b 05-jun-01 65,56 a 84,41 a 15,59 d Values with similar letters within the same fraction are not statistically different with 95% probability. 57 Appendix 2. Figures A1-A5: Phosphorus fractions as a percentage of Total Phosphorus Resin-P in % of TP 0 0,5 1 1,5 2 2,5 Depth (cm) 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 2000-11-11 80-100 Figure A1. Distribution of Resin-P in percentage of Total-P in the soil profile at five sampling occasions Bicarbonate-P in % of TP 0 10 20 30 40 50 60 Depth (cm) 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 2000-11-11 80-100 Figure A2. Distribution of Bicarbonate-P in percentage of Total-P in the soil profile at five sampling occasions. 58 Hydroxide-P in % of TP 0 10 20 30 40 50 60 Depth (cm) 0-20 2000-09-05 2001-04-15 20-40 40-60 2000-10-08 2001-06-05 60-80 2000-11-11 80-100 Figure A3. Distribution of Hydroxide-P in percentage of Total-P in the soil profile at five sampling occasions. HCl-P in % of TP 0 1 2 3 4 5 6 Depth (cm) 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 2000-11-11 80-100 Figure A4. Distribution of HCl-P in percentage of Total-P in the soil profile at five sampling occasions 59 Residual-P in % of TP 0 10 20 30 40 50 Depth (cm) 0-20 2001-04-15 2000-09-05 2001-06-05 2000-10-08 20-40 40-60 60-80 2000-11-11 80-100 Figure A5. Distribution of Residual-P content in percentage of Total-P in the soil profile at five sampling occasions 60 Bicarbonate OP and IP (% of Bicarbonate-P) Appendix 3. Figures A6-A13: Bicarbonate and Hydroxide Inorganic and Organic Phosphorus 100 90 b c ab ab b a bc c 2 3 c 80 70 60 50 40 30 20 a 10 0 1 Bicarbonate OP 4 Bicarbonate IP 5 Sampling occasions Bicarbonate OP and IP (% of Bicarbonate-P) Figure A6. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) in percentage of Bicarbonate-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 20-40 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 100 90 b a c d cd d c 80 70 60 50 40 30 20 ab ab b 10 0 1 Bicarbonate OP 2 Bicarbonate IP 3 4 5 Sampling occasions Figure A7. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) in percentage of Bicarbonate-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 40-60 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 61 Bicarbonate OP and IP (% of Bicarbonate-P) 100 90 b a a a b b 2 3 a a 80 70 60 50 40 30 20 b b 10 0 1 Bicarbonate OP 4 5 Sampling occasions Bicarbonate IP Bicarbonate OP and IP (% of Bicarbonate-P) Figure A8. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) in percentage of Bicarbonate-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 60-80 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 100 ab b c ab bc b a bc a 90 80 70 60 50 40 30 20 c 10 0 1 Bicarbonate OP 2 Bicarbonate IP 3 4 5 Sampling occasions Figure A9. Distribution of Bicarbonate Organic Phosphorus (Bicarbonate-OP) and Bicarbonate Inorganic Phosphorus (Bicarbonate-IP) in percentage of Bicarbonate-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 80-100 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 62 Hydroxide OP and IP (% of Hydroxide-P) 100 c b a d e d e b a 2 3 4 90 80 70 60 50 40 30 20 c 10 0 1 Hydroxide OP Hydroxide IP 5 Sampling occasions Hydroxide OP and IP (% of Hydroxide-P) Figure A10. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) in percentage of Hydroxide-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 20-40 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 100 90 d ab bc c a bc b 2 3 4 a 80 70 60 50 40 30 20 cd d 10 0 1 Hydroxide OP Hydroxide IP 5 Sampling occasions Figure A11. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) in percentage of Hydroxide-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 40-60 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 63 Hydroxide OP and IP (% of Hydroxide-P) 100 c c b a d c d a 3 4 90 80 70 60 50 40 30 20 b b 10 0 1 Hydroxide OP 2 5 Sampling occasions Hydroxide IP Hydroxide OP and IP (% of Hydroxide-P) Figure A12. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) in percentage of Hydroxide-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 60-80 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. c 100 90 a a b a c b c 80 70 60 50 40 30 20 c a 10 0 1 Hydroxide OP 2 Hydroxide IP 3 4 5 Sapling occasions Figure A13. Distribution of Hydroxide Organic Phosphorus (Hydroxide-OP) and Hydroxide Inorganic Phosphorus (Hydroxide-IP) in percentage of Hydroxide-P on five sampling occasions (where 1=5th September 2000, 2= 8th October 2000, 3=11th November 2000, 4=15th April 2001 and 5= 5th June 2001) at the depth of 80-100 cm. Mean values with similar letters within the same P fraction are not statistically different at 95% probability. 64 Appendix 4. Table A37: Weather data Table A37. Monthly precipitation and monthly average air temperature close to the sampling site for the periods of 2000 and 2001 (http://www.weather.vattenriket.kristianstad.se/cgiwin/vader.exe Month Precipitation (mm) Average air temperature (◦C) March 2000 52 1,7 April 42 9,3 May 36 13,3 June 123 15,5 July 51 16,8 August 49 16,2 September 62 13,0 October 67 11,7 November 95 7,6 December 46 3,4 January 2001 30 1,8 Februrary 21 0,2 March 21 1,4 April 42 9,3 May 28 13,3 June* 42 12,9 * The last sampling was 5th June, hence the precipitation and temperature shown in this table are values from the 1st – 5th June. 65 Appendix 5. Figures A14-A19: Photos of the site area Figure A15. Photo 1; Inundated sampling site, January 2001 (Photo by Ann Fristedt). road river/ ditch railroad photo direction Figure A14. Air photograph taken over the sampling site (Lantmäteriverket 1998. GSD- Digitalt Ortofoto dnr:507-983015). Arrows indicate photo direktions. Soil samples were taken where the arrow 2 is. Figure A17. Photo 3; Inundated adjacent fields, January 2001 (Photo by Ann Fristedt). 66 Figure A16. Photo 2; Knee-deep water at the sampling site, January 2001 (Photo by Emil Andersson). Figure A18. Photo 4; Inundated adjacent fields, January 2001 (Photo by Ann Fristedt).
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