Lake lowering in sulphide-rich areas is currently a major environmental impact for surface water. This study focuses on whether there is a relationship between a gradient of lake lowering and surface water impacts in areas of sulphide-rich sediments, in order to better understand their contribution of heavy metals and sulfuric acid. Also, is it a reasonable method to use the reduced lake area in order to quantify the gradient? The survey was conducted by collecting water samples from reference lakes and lowered lakes from south to north in coastal areas within the county of Västerbotten. Water samples were then analyzed for TOC, pH, conductivity, anions, base cations, alkalinity, acidity, sulfate, Al, Cd, Fe, Mn, Cu, Zn and Pb. These parameters were then compared statistically using regression analysis and t-tests. The results show that no gradient was discernible in response to the reduced lake area. However, significant differences (p < 0,05) between the reference lakes and all the reduced lakes were visible for pH, conductivity, Cd, Cu, Zn and Al. The study shows that there is a correlation between lake lowering and negative impacts on surface water. However, to calculate a gradient from the reduced lake area is deficient as it is limited by the lakes volume reduction, and how the area around the lake has been affected. Further studies on the subject are therefore necessary. / FLISIK (för livskraftiga småvatten i kvarkenregionen)

Acid sulfate soils covers an area area about 600 km-2 along the coast line of Northern Sweden. These soils originate from land uplift and oxidized sulfide soils. The oxidation process releases sulfur and Fe(III) and will lower the pH-value and mobilize metals that will cause toxic environments for water living organisms. Concerns of how higher occurrence of extreme weather conditions will affect the mobilization of metals has occurred. Understanding of the mobilizations of metals in different catchment conditions is therefore important knowledge for preparation of risk analyzes to protect ecosystems from toxic effects. The aim of this study is to compare accumulation of metals in sediments from marine and limnic environments to investigate how lakes effects the mobilization of metals in catchments consisting of acid sulfate soil. Answering the questions of accumulation differences between the catchments and how organic matter affects the mobilization and accumulation of metals. Sediment cores were collected in two different catchment areas, known to be affected by acid sulfate soils, in Västerbotten county. 22 different elements were analyzed by x-ray fluorescence spectroscopy and Loss-on-ignition (LOI) was used as a proxy for organic matter. The results indicate that draining of land areas, often due to agriculture and deforestation, increases mobilization and accumulation of metals correlated with both organic and lithogenic fractions to a large extent. However, elements such as S, Ni, Zn, Fe, Cu, Na, Mg, Al, Rb, Sr and Zr are derived from mobilization from acid sulfate soils where elements with high correlation with organic matter accumulates in limnic environment conditions.

Ce projet de thèse vise à étudier les processus géochimiques de l'aluminium dans les sols acides à sulfates. Les résultats obtenus avec le dispositif de dialyse de Donnan montrent que l'aluminium dans la solution du sol est presque exclusivement (> 98%) présent sous forme de complexes de charge négative, vraisemblablement des organo-complexes d'aluminium. Les concentrations d'aluminium isotopiquement échangeables (valeurs-E) et les concentrations obtenues par extractions chimiques révèlent qu'une solution de 1 M KCl sous-estime systématiquement les valeurs E. Une méthode d'extraction séquentielle a révélé qu'une quantité importante de minéraux primaires (initialement présents dans les sols) a déjà été dissoute, comme en témoignent les concentrations élevées d'aluminium présentes en tant que minéraux secondaires d'aluminium. Ces études permettent de mieux comprendre la géochimie de l'aluminium dans les sols CLASS et de pouvoir intégrer ces connaissances dans la gestion des sols. / The aim of this thesis was to further understanding on Al geochemistry in coastal lowland acid sulfate soils (CLASS). It was observed that Al was present almost solely (> 98%) as negatively charged complexes in CLASS pore-waters, presumably with natural organic matter. Isotopically exchangeable concentrations (E-values) of Al and extraction solutions used to estimate the exchangeable pool showed that 1 M KCl always underestimated isotopically exchangeable Al concentrations in these soils and that 0.2 M CuCl2 improved agreement between both methodologies but sometimes overestimated corresponding E values. A sequential extraction procedure showed that substantial amounts of Al have already been dissolved from primary aluminosilicates initially present in the soils and remain in the soils mostly as reactive secondary Al minerals. The outcomes of this thesis significantly further our understanding of Al geochemistry in CLASS environments and how this knowledge can be incorporated into land management practices.

In the north of Sweden lots of the soil is naturally contaminated by acid sulfate. When soil gets in contact with oxygen an oxidation process begins which releases elements that may be harmful to the surroundings. When the Botniabanan was built, soil had to be transported from the railroad area to deposit sites. This study was made to investigate the suspicions a landowner had regarding if his estate had been contaminated sulphide soil soil during the building of the Botniabanan. To do that four pits were dug in the area where the soil had been deposited. Then the soil was analyzed to see the content of sulfate, iron, organic matters and water. When the results was compared to other studies it showed that the content of sulfate and organic matters was to low to classify the soil as an acid sulfate soil.

Marine sulfide – bearing sediments that oxidize when in contact with oxygen and leach outelements in high concentrations to small watercourses have been a problem for many years allover the world especially around the Bothnian Bay. The purpose of this study was to furtherinvestigate the sulfur mineralogy present in acid sulfate soils in the area of Luleå, Sweden. Asecondary aim was to see if elements leach out and accumulate in an acid sulfate soil closer tothe recipient. Samples were taken in two profiles (one oxidized and one waterlogged) fromfour sites (sites A-D) and were analyzed for whole rock geochemistry. Two sites were furtherinvestigated for mineralogy in polished samples with an optical microscope, Ramanspectroscopy and SEM-EDS. Each profile consisted of three layers: oxidation zone, transitionzone and reduced zone. The oxidation zone above the groundwater table was light grey withbrown iron hydroxide staining. Parts that lied under the water table were dark grey-black within general strong odor (“rotten eggs”) due to its sulfur content. It was usually straightforwardto distinguish and separate the layers from each other directly in the field, however in somecases pH was needed for confirmation.A general feature of investigated polished samples is the presence of abundant framboidalpyrites that are common in reduced marine sediments. The transition zone was formed in suboxicconditions and this feature is reflected by the mineralogy. Many morphologies of theframboidal pyrite were observed in this layer and signs of both dissolution and formationoccur. In the sample from site C one could observe elemental sulfur in form of large (up to 50μm) euhedral crystals. In the samples with pH<4, no sulfides occur as they have been replacedby jarosite (site B). Site C lacks these sulfur-bearing hydroxides which is thought to be due toa sulfur concentration of <0.2 %. Sulfur shows extensive leaching at most sites but at site B andD1, it accumulates in the transition zone. Elements like cobalt (Co), nickel (Ni) and zinc (Zn)are leached out or are accumulated further down in the profile. Elements that could have beentransported and have accumulated in the waterlogged profiles are Co, Ni, Zn and chromium(Cr) and in some profiles also copper (Cu) and vanadium (V). / Coastal watercourses in Bottenviken: Method development and ecological restoration- A cross-border Swedish-Finnish cooperation project

Casamance is a region in southern Senegal that traditionally produces rainfed rice, but Senegal produces only 1/3 of its rice consumption. Lowland areas, where rice is primarily produced, have acid sulfate soils with low pH and potential aluminum and iron toxicity. The goal of this work was to determine if soil amendments can alleviate soil acidity, counteract the negative biogeochemical effects that occur in flooded conditions, and increase rice yield. A two-year experiment was conducted to test the following soil treatments – agricultural lime, pulverized oyster shell, biochar, and control (no amendment) – in flat and raised beds. Plots amended with lime and shell materials had increased soil pH, base saturation, Ca, and cation exchange capacity. Meanwhile, biochar elevated particulate organic matter and C:N ratios. Exchangeable Fe and Al were negatively correlated with soil pH, while Geobacteraceae populations (Fe reducing bacteria) increased with pH. A greater proportion of the total Fe was strongly bound in fractions that were less bioavailable in plots amended with shell or lime, and overall rice yields were significantly higher following amendment with shell or lime. During the second growing year these effects diminished, suggesting that liming effects did not persist as expected. These results demonstrate the benefits of soil amendments that raise soil pH and suggest that this effect operates by influencing overall soil nutrient availability to rice plants, but further research is needed regarding the timing and sustainability of the beneficial liming effect. / Master of Science

One of the modern times worst environmental problem are polluted water resources. An example of source of pollution to water resources are, heavy metal leached from acid sulfate soils (ASS). When these soils are stable, which they are if they are left underwater in an anoxic environment (for example below the water table), they are often sought after since they consist of high amount of nutrients which farmers use as farmlands. ASS is therefore created when farmers drain their land and the sulfide soil gets exposed to air, resulting in its oxidation and therefore formation of sulfuric acid. In a previous study performed by scientists from Linnaeus University, it was concluded that a natural reserve located in Vattenriket, Kristianstad was possibly damaged by the drainage discharge of an adjacent acid sulfate soil. For remediation of acid sulfate soil, notably removal of metals from drainage waters, grounded coffee has been suggested to be able to perform well as an adsorbent. This study was performed to investigate how well grounded coffee could be used as an adsorbent, for calcium (Ca) and zinc (Zn), from water samples collected in Vattenriket, Kristianstad. It was also studied to see if grounded coffee could be cleaned using a sodium hydroxide solution to increase its adsorption capacity. To be able to evaluate how well it could be used as an adsorbent, it went through two different cleaning procedures and total organic carbon and pH readings was performed. The used method for this paper was to clean the grounded coffee in two different stages. The first stage consisted of using distilled water and letting it run through the residues until the water came out as transparent. Cleaning using a NaOH solution consisted of suspending the residues in a NaOH solution for 45 minutes and swapping the solution 6-8 times. After the grounded coffee had dried in an oven at 30o for 48 hours, it was put into different fraction sizes, weighed and bagged. The water samples then had to be filtered using a pump and Filtropur S 0.45 filters. Lastly, 45 falcon tubes containing 15 different amounts of grounded coffee had 50 ml of filtered water sample added to them. For analysis, atomic absorption spectroscopy was used. The results showed that the maximum amount of adsorbed calcium was achieved at 1.5g of grounded coffee in a 50 ml water solution which managed to adsorb 99.53% of calcium. The maximum amount of adsorbed zinc was achieved at 1.25g of grounded coffee in a 50 ml solution which resulted in 99.16% of adsorbed zinc. The study also showed that when the total organic carbon-content was decreasing, due to excessive cleaning, the pH was increasing. This was further proof that the grounded coffee still had residues onto its surface that could inhibit its adsorption capabilities.

Sediments rich in sulfide were deposited in the Littorina sea in an environment that was shallow, anoxic,and reductive. The sediments were brought above sea level by isostatic uplift and can now be foundalong the coast of the Baltic sea. These sulfide rich sediments oxidize when they are exposed to air whenthe water table is lowered due to uplift, anthropogenic activities, or hydrological droughts. Oxidation ofsulfate soils will lower the pH and mobilize metals in the soil that will leach into adjacent rivers and willimpact the water chemistry and damage ecosystems. A few studies have noted that leaching increasesin sulfate soils after drought which has resulted in fish death. The impact of droughts on leaching from sulfate soils were investigated in nine rivers (Flarkbäcken,Hertsångerälven, Kvismare canal, Kyro river, Närpes River, Persöfjärden, Storbäcken, Tjuståsaån, andToby river) by looking at time series of sulfate concentrations and drought periods. The impact on riversafter a drought was studied by plotting the deviation from median specific discharge in summer andautumn against the deviation from median concentration of SO42-, a suite of metals and pH the followingseason with high discharge e.g. spring. The metals that were examined in the river were Aluminum (Al),Cadmium, (Cd), Cobalt (Co), Cupper (Cu), Iron (Fe), Manganese (Mn), Nickle (Ni), Zinc (Zn).TheKendall’s τ was then used to determine if the relationship between discharge and leached compoundconcentration was significant and which direction it had. In the sulfate timeseries the hydrological droughts generally coincided with low SO42- and werefollowed by SO42- peaks. The sulfate concentrations increased significantly after droughts, and theincrease in SO42- lasted for 1-3 years for most rivers. In two Finnish rivers the SO42- remained higher alonger time of 5 years in Kyro river and Närpes river after multiyear droughts. In Kvismare canal, Kyroriver, Närpes river and Tjuståsaån the SO42- concentration was higher in the mid-1900s which could bedue to changes in ditching activity, the acid sulfate soils transitioning to post active sulfate soils afterthe ditching activity stopped in the regions, or SO42- air deposition historically being greater. SO42-, Co, Ni, and Zn had negative significant correlations in a majority of the rivers, while pH, Fe,and total organic carbon had significant positive correlations a majority of rivers. A negative correlationindicates high concentrations of the leached compound after a drought while positive correlationsindicate low concentrations of the leached compound after a drought. Al, Cd, Cu, and Mn did not havea significant correlation in a majority of the rivers which could be due to their dependence on pH whichwill not always change in the rivers in spring due to acidic water leaching from acid sulfate soils sincethe acidic water will be diluted by meltwater. / Efter senaste istiden var vattnet i havet syrefritt och reducerande vid havsbotten, vilket ledde till attsulfidmineral avsattes. Dessa sulfidrika sediment har hamnat ovanför havsytan på grund avlandhöjningen och finns i kustnära områden runt östersjön. Sulfidsedimenten oxiderar om de kommer ikontakt med syre vilket kan ske på grund av landhöjning, mänskliga aktiviteter, eller torka som sänkergrundvattennivåerna. När sulfatjordarna oxiderar sänks pH i jorden och metaller frigörs vilka sedanlakas ur jorden och påverkar närliggande vattendrag och ekosystem. Lakning av metaller har i någrastudier setts öka efter extrem torka vilket i vissa fall har lett till fiskdöd. I nio vattendrag (Flarkbäcken, Hertsångerälven, Kvismare kanal, Kyro älv, Närpes å, Persöfjärden,Storbäcken Tjuståsaån och Toby å) undersöktes hur torka påverkar urlakning från sura sulfatjordar. Deämnen som undersöktes var Aluminium (Al), Kadmium (Cd), Kobolt (Co), koppar (Cu), Järn (Fe),Mangan (Mn), Nickel, (Ni), Totalt Organiskt Kol (TOC), och Zink (Zn). Sambandet mellanvattenföringens avvikelse från medianen under de sommar samt höst och avvikelsen avkoncentrationerna av urlakade ämnen från medianen följande årstid med högt flöde plottades för attundersöka hur sambandet såg ut. De statistiska testerna Kendalls τ användes för att utvärdera om enkorrelation existerade och i vilken riktning den gick. Sulfatkoncentrationerna var generellt sett väldigt låga under torrperioder men ökad snabbt efter atttorkan avtagit. Den förhöjda sulfatkoncentrationen varade generellt sett i 1-3 år för de flesta vattendrag.Det fanns däremot två undantagsfall då sulfatkoncentrationerna var förhöjda i Kyro älv och Närpes åunder 5 år efter en torrperiod som varat i flera år. I Kvismare kanal och Tjuståsaån varsulfatkoncentrationerna, högre under mitten av 1900-talet. De högre koncentrationerna av sulfat kanbero på att det var mer dikning, eller större mängd luftföroreningar under denna period. Sambanden för sulfat, Co, Ni och Zn visade att efter torra perioder var koncentrationerna högre i enmajoritet av vattendrag än normalt. pH, Fe och TOC visade på ett motsatt samband. Efter torrperiodersjönk därmed koncentrationen Fe och TOC i en majoritet av vattendragen. Al, Cd Cu, och Mn hadesignifikanta samband i mindre än 50 % av vattendragen vilket kan vara till följd av att de är beroendeav pH som själv inte hade en tydlig korrelation i alla vattendrag. pH sjunker i många fall inte särskiltmycket till följd av en torka då vattnet som lakas ut från sulfatjorden späds ut av smältvatten undervåren.

I Fredriksdalsvikens naturreservat i Kristianstads kommun skedde omfattande metalläckage efter en översvämning sommaren 2007 som orsakade skador på djur- och växtliv. De kraftiga metalläckagen misstänks härledas till sura sulfatjordar. Sura sulfatjordar tillhör de miljöskadligaste jordarna i världen på grund av de kraftiga metalläckagen och försurningen som jordarna orsakar till omgivningen. Mot bakgrund till humusämnens centrala roll för metalltransport i naturliga miljöer, syftade denna studie till att kartlägga hur organiskt kol är fördelat, sprids samt hur det kan förklaras i ett område nära det drabbade naturreservatet. Studien är en del av ett pågående forskningsprojekt i området som bedrivs på Linnéuniversitetet. I studiens undersökningsområde dominerar jordbruksmark som dräneras av ett dikessystem från norr till söder. Vattnet som avleds i dikessystemet pumpas slutligen till en våtmark i Fredriksdalsvikens naturreservat. I studien analyserades jord från åkermark, dikessediment, porvatten och dikesvatten från området på totalt organiskt kol med metoderna glödförlust och kyvett-test. Totalhalterna jämfördes med pH och grundvattennivå i åkermark. Resultat och slutsatser av studien är att högst halter löst organiskt kol uppmättes i dikesvattnet uppströms i dikessystemet och beror troligtvis på bottenfauna som inte växer i andra delar av systemet. I dikessediment ökar den organiska halten nedströms i dikessystemet och kan förklaras genom tillförsel av organiskt kol från två diken som dränerar åkermark rik på organiskt kol. De högsta halterna organiskt kol i jord beror på ett tunt torvlager. I åkermark visar inte resultaten någon tydlig statistisk korrelation mellan pH och totalt organiskt kol, men kraftig pH-sänkning tillsammans med höga totalhalter organiskt kol i torvjord beror troligtvis snarare på humusämnen än på sur sulfatjord. I åkermark väster om dikessystemet ökar den organiska halten med djupet under grundvattenytan. I samma åkermark ökar halterna av totalt organiskt kol lateralt mot dikessystemet, parallellt med att pH sjunker som troligen påverkas av starkare bindningsmekanismer till mineral, lägre mikrobiell aktivitet och minskad urlakning av löst organiskt kol. Men fler undersökningar i området krävs då markanvändning, erosion, jordarternas textur och sammansättning samt vattnets spridningsvägar också är avgörande faktorer för fördelning och spridning av organiskt kol i naturliga miljöer. / In the nature reserve Fredriksdalsviken in Kristianstad municipality, extensive metal leakage occurred after a flood in the summer of 2007 that caused damage to wildlife and plant life. The heavy metal leaks are suspected to be derived from acid sulphate soils in the area. Acid sulphate soils are among the most environmentally harmful soils in the world due to its extensive acidification and leaching of metals to the environment. In the light of humic substances key role for metal transport in natural environments, this study aimed to investigate how organic carbon is distributed, spread and how it can be explained in an area near the affected nature reserve. The study is part of an ongoing research project in the area conducted at Linnaeus University. The study area is dominated by agriculture land which is drained by a ditch system from north to south. The drained water in the ditch system is finally pumped to a wetland in the Fredriksdalsviken nature reserve. In the area, total organic carbon was analysed on soil from arable land, ditch sediment, pore water and ditch water with the methods loss of ignition and cuvette-test. Total levels were compared with pH and the groundwater level in arable land. The results and conclusions of the study are that the highest content of dissolved organic carbon in the ditch water upstream the ditch system is probably due to benthic fauna that doesn’t grow in other parts of the system. In the ditch sediment, the organic content increases downstream in the ditch system and can be explained by the supply of organic carbon from two ditches that drain arable land rich in organic carbon. In arable land are the highest levels of organic carbon due to a thin peat layer. The results does not show a clear statistical correlation between pH and total organic carbon in soil, but a sharp decrease in pH together with high total levels of organic carbon in peat soil is probably due to humic substances rather than to acid sulphate soil. In the western arable land of the ditch system, levels of total organic carbon increase laterally towards the ditch system at the same time as the pH decreases, which is probably affected by stronger binding mechanisms to minerals, lower microbial activity and reduced leaching of dissolved organic carbon. However, more research is required in the study area, since land use, erosion, soil texture and constitution together with the flow paths of water also are crucial factors for the distribution and pathways of organic carbon in natural environments.