Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) have been assigned toxic equivalency factors (TEFs). These compounds are today routinely analysed with sophisticated analytical techniques. In a near future, there might be other dioxinlike compounds such as polychlorinated naphthalenes (PCNs), alkyl-polychlorodibenzofurans (R-PCDFs), and polychlorinated dibenzothiophenes (PCDTs) added to this list of toxic dioxin-like compounds. It is therefore important to have a readiness to analyse these new compounds in environmental samples. In this study, a multi-residue non-destructive analytical method for the analyses of these planar dioxin-like compound classes was developed. The use of HPLC PX-21 carbon column fractionation enabled the separation of interfering PCBs from coplanar PCBs and other planar dioxin-like compounds of interest. The obtained planar fraction containing the dioxin-like compounds was analysed using high-resolution GC-MS. Levels of PCNs in surface sediments and settling particulate matter in the northern Baltic Sea were determined. The concentrations of PCNs in background surface sediments were approximately 1 ng/g dw and the estimated PCN fluxes were similar to the pre-industrial levels determined in Europe. The PCN congener patterns in the surface sediments suggest that the PCNs deposited in the Baltic Sea originate from similar sources. Bioaccumulation of PCNs in a benthic food chain (sediment, amphipod, isopod, and four-horned sculpin) from the Gulf of Bothnia was studied. The results indicated that only a few PCN congeners biomagnified. The highest biomagnification factors (BMFs) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms. The calculated biota to sediment accumulation factors (BSAFs) showed that the tetra- and penta- CNs exhibited BSAF values higher than one, while BSAFs for the more chlorinated PCNs were less than one. A general difference between the northern and southern parts of the Gulf of Bothnia could be seen in the samples, with the lowest PCN and total PCB concentrations being found in the north and the highest in the south. This gradient is related to distance from the more industrialised and populated regions in the southern parts of Sweden and Finland, and central Europe. Analysis of R-PCDFs in crustacean samples from the Swedish west coast was performed using HRGC-MS/MS. The ΣR-PCDFs in these samples were present at concentrations up to 10 times higher than the ΣPCDFs. The relatively high concentrations of R-PCDFs in the crab samples demonstrate that these compounds bioaccumulate. The fate of a pollutant in the environment and the toxicity of a compound are governed by its physicochemical properties. The information found in a data set of properties can predict a compound’s mode of action. The following physicochemical properties for 87 PCDFs were measured: ultra-violetadsorption, relative retention times on two common gas chromatographic stationary phases, and relative mass spectrometric response factors using EI- and NCI- modes.

BIOGAS POTENTIAL IN GRASSES FROM WETLANDS Marvin Martins The purpose of this study has been to survey wetlands that are suitable for mowing and to analyze the biogas potential in the harvested grasses. A preformed investigation showed that there are suitable wetlands, which can be harvestable, namely those mowed formerly in traditional haymaking. The practice of traditional haymaking is dying out in Sweden today but there are several good reasons why it should to be reconsidered. Nature- and cultural values are obvious, also the unutilized energy in the grass. The suitable types of wetland that were specifically studied were the productive wetlands; meadow marshes and wet meadows. These wetlands are represented in the Swedish meadow- and pasture inventory database; (TUVA) and the Swedish national wetland inventory (VMI). Going through the databases showed that they largely complement each other. A geographical mapping was also carried out of wetlands in relation to areas of interest for the future establishment of biogas plants, so called “hotspots”. The geographical survey shows that there is ample amount of grass from wetlands within a 30-kilometer radius that can supplement the plants main substrate, manure. The map layer Swedish Ground Cover Data (SMD) together with GIS software was used to analyze the extent of overgrowth for the older VMI objects in Uppsala County, with the result that half of the VMI objects are no longer of interest. They have become either woodland and bogs, or reed beds. There is very little information on wetland-grasses and methane production. Instead, a theory was evaluated regarding the possibility of transforming nutritional values for grass and sedges into biogas potentials. It was shown that this method does not capture the total biogas potential, but offers a minimum value that can be considered rather reliable. The energy transformation showed that late harvested grasses from wetlands has a biogas potential about 0, 21Nm3 methane/ (kg, DM) which is about 60 % of the biogas potential for grass-legume forages. The gas yield after 20 days is also relatively low. It could though be favorable to try grasses from wetlands in methane production, because co-digestion with these grasses and other suitable materials could produce a higher net gas yield for the plant, than using the materials solely by themselves. The derived biogas potential showed that there is at least 4, 4 GWh biogas energy in grasses from wetlands in Uppsala county at a low estimate. Harvesting costs were however shown to be too high in the present to achieve a plus result. / BIOGASPOTENTIAL HOS VÅTMARKSGRÄS Marvin Martins Syftet med detta arbete har varit att kartlägga våtmarker i Biogas Östs region lämpliga att skörda samt att undersöka biogaspotentialen i detta våtmarksgräs. Undersökningen visar att det finns lämpliga våtmarker, så kallade slåtterängar, i den undersökta regionen. Traditionell slåtter är en utdöende företeelse i Sverige men det finns flera goda argument till varför den borde återupptas. Natur- och kulturvärden är givna sådana men även den outnyttjade energin i gräset. Våtmarkstyper som specifikt har studerats är de produktiva våta slåtterängarna; fuktängar, strandängar och mader. Dessa våtmarker finns representerade i Ängs- och betesmarksinventeringens databas; TUVA och våtmarksinventeringens VMI. En genomgång av databaserna visade att de i stor utsträckning kompletterar varandra. En geografisk kartläggning har även utförts på slåttermarker i förhållande till intressanta områden för framtida biogasanläggningar, så kallade ”hotspots”. Kartläggningen visar att det finns gott om våtmarksgräs inom en tremilsradie som kan komplettera anläggningarnas huvudsubstrat, gödsel. Kartskiktet Svenska Marktäckedata (SMD) tillsammans med GIS-programvara har använts för att analysera hur mycket de äldre VMI-objekten i Uppsala län har växt igen, med resultatet att hälften av VMI-våtmarkerna är inaktuella i dagsläget. De har antingen växt igen med mossor och träd eller blivit vassbälten. Det finns ytterst begränsat med information kring rötdata på våtmarksgräs. Istället utvärderades en teori, om fodervärden för ett par gräs- och starrarter kan omvandlas till biogaspotentialer. Det visade sig att denna metod inte ger den maximala biogaspotentialen men ett minimivärde erhålls som kan betraktas som ganska tillförlitligt. Energiomvandlingen visar att sent slåttat våtmarksgräs har en biogaspotential runt 0,21 Nm3 metan/(kg, TS) vilket är omkring 60 % av den odlade åkervallens biogaspotential. Gasutbytet efter 20 dagars rötning är också relativt lågt. Trots detta kan det vara fördelaktigt att röta våtmarksgräs, eftersom samrötning mellan detta och annat lämpligt material kan ge ett högre nettogasutbyte för anläggningen än rötning av de enskilda materialen var för sig. Den framtagna biogaspotentialen visar att det finns minst 4,4 GWh biogasenergi i våtmarksgräs från till exempel Uppsala län, lågt räknat. Slåtterkostnaderna har dock visat sig vara för höga för att få det att gå ihop ekonomiskt i dagsläget.

Negative effects on water quality are created by eutrophication of the world’s water resources. Mitigation measures have been implemented, but poor improvements in water quality have been observed. Two-stage ditches have the possibility to increase nutrient and sediment retention to reduce eutrophication in receiving water bodies. A two-stage ditch has floodplain terraces on each side of the ordinary main channel. The terraces are available for flooding during high water flows and enables decreases in flow velocities. However, more knowledge is needed about the two-stage ditch and its effect in Swedish landscapes. The aim of the project was to study the two-stage ditch design with focus on water retention. Optimization of the two-stage ditch design was made by modeling and simulating design parameters and vegetation in the software Hydrologic Engineering Center’s River Analysis System (HEC-RAS). An existing two-stage ditch in Sweden was used as base and comparison to the theoretical model. In addition, a climate change scenario was studied to evaluate the impact of increased storm events in a two-stage ditch. Results showed that increased retention time of water, nutrients, and sediments theoretically can be given by designing two-stage ditches with maximum terrace width and minimum terrace height, and with terraces angled away from the main channel. Vegetation should also be kept on both terraces and in the main channel of the two-stage ditch to increase retention time. The study also showed that the two-stage ditch design has the possibility to decrease peak water levels during storm events, which can be expected to increase in the future. The impact on transport of nutrients and sediments from more future extreme hydrological events needs further studies. / Negativa effekter i vattenkvalitet skapas av övergödning i världens vattenresurser. Åtgärder för att begränsa övergödningen har genomförts, men svaga förbättringar i vattenkvalitet har noterats. Tvåstegsdiken har möjligheten att öka retentionen av näringsämnen och sediment för att minska övergödning. Ett tvåstegsdike har terrasser på vardera sida om den vanliga mittfåran. Terrasserna är tillgängliga för översvämning vid höga vattenflöden, vilket möjliggör minskning av flödeshastigheter. Dock krävs mer kunskap för tvåstegsdiken och dess effekt i svenska landskap. Syftet med projektet var att studera designen av tvåstegsdiken med fokus på retention av vattenflöde. Optimering av tvåstegsdikens design genomfördes via modellering och simulering av designparametrar och vegetation i programvaran Hydrologic Engineering Center’s River Analysis System (HEC-RAS). Ett befintligt tvåstegsdike i Sverige användes som bas och jämförelse mot den teoretiska modellen. Ett scenario för klimatförändring studerades även för att utvärdera effekten i ett tvåstegsdike då fler stormevent sker. Resultaten visade att ökad retentionstid for vatten, näringsämnen, och sediment teoretiskt kan ges genom att designa tvåstegsdiken med maximal terrassbredd och minimal terrasshöjd, samt med terrasser vinklade bort från mittfåran. Vegetation bör även behållas på terrasser och i mittfåran av tvåstegsdiket för att öka retentionstiden. Studien visade även att tvåstegs- dikets design har möjligheten att minska toppflöden vid stormevent, vilka kan förväntas öka i framtiden. Påverkan på transport av näringsämnen och sediment från fler framtida extrema hydrologiska event kräver ytterligare studier.

Au cours des dernières décennies, une grande variété de pesticides émergents, tels que le chlorantraniliprole (CAP), ont été introduits malgré le manque de connaissance approfondie de leur risque écotoxicologique. Les marais filtrants (TW) sont des technologies écologiques et durables qui ont montré un grand potentiel d’atténuation des polluants agricoles communs, tels que les pesticides dans le ruissellement. L’objectif de cette étude était d’optimiser l’utilisation du marais filtrant sous-surfacique à écoulement horizontal (HSSF) en déterminant: a) l'effet d’un amendement de biochar au substrat et b) la performance de trois espèces de macrophytes (Phragmites australis subsp. americanus, Scirpus cyperinus et Sporobolus michauxianus) dans l'abattement du CAP du ruissellement agricole. L'efficacité d'abattement a été calculée en utilisant la méthode du bilan de masse dans des mésocosmes HSSF matures alimentés avec un ruissellement agricole synthétique contenant du CAP pendant une période d'un mois. Les mésocosmes avec l’ajout de biochar se sont avérés très efficaces dans l’abattement du CAP (90 à 99%) et ils le sont restés tout au long de la période expérimentale. Cette efficacité est probablement due à la grande capacité d’adsorption du biochar, bien que ce mécanisme n’ait pas été directement mesuré. En revanche, l'abattement du CAP dans les mésocosmes plantés sans biochar était faible et limité et il n’y avait pas de différence entre les espèces, bien qu’elles aient eu des différences dans leur biomasse aérienne et leur taux d'évapotranspiration (ET). Cependant, les traitements plantés ont agi comme zone tampon, en atténuant la masse du CAP de l'influent et en la libérant lentement dans l'effluent. Le taux d'ET de Scirpus et Phragmites était plus élevé que celui de Sporobolus, ce qui s’est traduit par un meilleur effet tampon. Cette étude suggère que l'ajout de biochar au substrat HSSF TW est prometteur pour l'atténuation du CAP dans le ruissellement agricole, mais leur efficacité à long terme reste à être étudiée. Malgré tout, les TW devraient être utilisés comme un outil complémentaire, dans le cadre d'actions plus larges visant à réduire la pression des polluants sur les écosystèmes aquatiques. / Over the past decades, a wide variety of emergent pesticides, such as chlorantraniliprole (CAP), have been introduced despite the lack of in-depth knowledge of their ecotoxicological risk. Treatment wetlands (TWs) are environmentally friendly and sustainable technologies that have shown great potential to mitigate common agricultural pollutants, such as pesticides in runoff. The objective of this study was to optimize the use of the horizontal subsurface flow treatment wetlands (HSSF TWs) by determining a) the effect of biochar amendment to the substrate and b) the performance of three species of macrophytes (Phragmites australis subsp. americanus, Scirpus cyperinus and Sporobolus michauxianus) in CAP removal from agricultural runoff. The removal efficiency was calculated using the mass balance method in mature HSSF mesocosms fed with synthetic agricultural runoff containing CAP for a period of one month. Mesocosms with the addition of biochar were very effective in removing CAP (90-99%) and remained so throughout the experimental period. This efficiency is likely due to the high adsorption capacity of biochar, although this mechanism has not been directly measured. In contrast, CAP removal in mesocosms planted without biochar was low and limited and there was no difference between species, although there were differences in their above-ground biomass and their evapotranspiration (ET) rate. However, the planted mesocosms acted as buffer zones, reducing the CAP mass of the influent and slowly releasing it into the discharge. The ET rate of S. cyperinus and P. australis was higher than that of S. michauxianus, resulting in a better buffering effect. This study suggests that adding biochar to the HSSF TW substrate is promising for CAP attenuation in agricultural runoff, but their long-term effectiveness remains to be investigated. Nevertheless, TWs should be used as a complementary tool, as part of wider actions aimed at reducing the pressure of pollutants on aquatic ecosystems.