The harbour land fill in Halmstad has been described in the news as one of the most polluted areas in Halland County based on the a survey from the Swedish environmental protection agency. In order to identify the extent and severity of the situation several environmental investigations have been performed in this area. This report is based on available data from investigations and environmental reports from WSP, Höganäs AB, HEM and Halmstad municipality. This investigation focus on an “Area C” within the land fill where the main land fill material is i.a. slag from a steel work, construction waste, dredge spoil, waste from glass production and a casting shop. Of these material the focus have been on the metal rich slag from the steel work and its possible environmental impact. The environmental exposure of Hg, Pb, Cd, Cr, Zn, Ni, Mo and V have been calculated as an annual load from Area C. Unfortunately the data available for this investigation has not been complete, e.g. slag concentration data with corresponding leachate data was only obtained for one year. The groundwater data and land fill metal concentrations have been measured only once. This made it impossible to investigate e.g. annual variations like ageing effects of the material or weather variations, variation in the properties of the deposed slag material and statistical significance in differences could not be calculated. Further characterisation of the land fill would be worthwhile in order to be able to draw some conclusions. Calculations of the environmental load has been performed based on concentration in the slag, the land fill, the leachate data of the slag and groundwater concentrations. A model has been developed to calculate the weighted land fill metal concentration. The partitioning coefficient, Kd; between soil and liquid has been calculated and used to estimate the environmental load. It was assumed that the groundwater data was the most reliable data, which indicated that the exposure may be higher than from common soil, especially for Pb and Mo. Relating the environmental exposure values with guideline values based on MKM (less sensitive land use)-land using HQ (hazard quotient) indicates a decreasing risk in the order Pb>V>Mo. However, the exposure is well below that from MKM soil which could be assumed, according to Swedish environmental protection agency guideline values, to be an acceptable exposure.

Kate Valley is a municipal waste landfill situated in Waipara, Northern Canterbury. It is a joint venture between the 6 local regional councils and Transwaste Canterbury Ltd to help dispose of waste quantities generated in the wider Canterbury region. Landfill waste disposal also generates waste streams. Major waste streams can include methane gas production and liquid leachate. One practice which can turn liquid leachate waste streams into a nutrient source for plants is land irrigation. It is important to have a thorough understanding of the interactions involved with leachate, soil structure, soil microbiology, flora. This thesis investigates the sorption mechanisms between Kate Valley soil and leachates, through batch and column experiments. Sorption mechanisms between leachate and soil were investigated through batch and column tests. Ex-situ soil samples were extracted from Kate Valley, along with raw leachate samples for batch tests at a soil to liquid ratio of 30 g vs. 70 ml respectively. Tested dilution leachate strengths ranged from raw to 50x raw leachate dilution; meanwhile soil samples were categorized into 3 groups based on soil depth: 0-20 cm, 20-40 cm, and 40-60 cm. Column tests were conducted on 3 extracted in-situ soil column monoliths. Column test irrigation conditions included: control case, 2x and 10x raw leachate dilution, and 200 mg/L KBr (bromide column), where the same soil column was used for bromine testing after control testing had ceased. Batch results suggest deeper soils are less effective at sorption of ammonia, where partitioning coefficient ranged from 9.5x*10-7 to 6.4*10-7 L/mg for 0-20 cm soil to 40-60 cm soil respectively. Column results generally showed lower partitioning capacity than batch results, at 4*10-8 and 5*10-8 L/mg for 10x and 2x dilution leachate irrigation respectively. Discrepancies in experimental data have been attributed to: different dilution leachates tested between batch and column tests, making it difficult for direct comparison; extreme soil to liquid ratios employed in experiments; direct data comparison between the “full-contact” experimental data (between leachate and soil), obtained from batch tests with column results, where not all soil may have been fully exposed for shrinkage of boundary layers of soil particles; and oxygen exposure of samples during testing and sampling, possibly encouraging nitrification.

L’aérosol organique secondaire (AOS) est issu de processus d’oxydation des précurseurs gazeux, les composés organiques volatils (COV). Des lacunes persistent encore dans la connaissance des voies de formation et d’évolution de l’AOS et de sa composition chimique à l’échelle moléculaire. Ces différents aspects expliquent en partie la sous-estimation de sa concentration globale par les modèles. Pour apporter des éléments de réponse à ces problématiques, le bassin méditerranéen a été sélectionné comme région d’étude. Celui-ci est, en effet, caractérisé par une forte photochimie, notamment en été, et des sources de COV très intenses, à la fois biogéniques et anthropiques, réunissant ainsi les conditions favorables à la formation d’AOS dans l’atmosphère. Dans ce contexte, deux campagnes de mesures ont été réalisées dans le cadre des programmes Canopée et ChArMEx.Grâce au déploiement d’une méthode de prélèvement et d’analyse par TD-GC/MS, la caractérisation de la fraction organique a permis la détermination de plus d’une centaine de composés oxygénés de C2 à C18 en phases gazeuse et particulaire. La complémentarité des jeux de données obtenus avec des méthodes plus traditionnelles (PTR-MS, AMS) a permis d’apporter des éléments de réponse sur la réactivité des composés oxygénés vis-à-vis du radical OH, sur la composition de la matière organique sur deux sites aux caractéristiques contrastées et sur la propension de différents précurseurs biogéniques et anthropiques à former de l’AOS. La détermination des coefficients de partage théoriques et expérimentaux apportent également des éléments de réponse quant à la représentation de l’AOS dans les modèles / Secondary Organic Aerosol or « SOA » is formed in the atmosphere by oxidative process of volatile organic compounds (VOC). Gaps in knowledge of SOA formation and evolution pathways and of molecular characterization still exist. These aspects are an important source of uncertainties and can explain the underestimation of SOA budget calculated by models. In order to give new insights on these issues, the Mediterranean basin appears like an ideal area to study SOA. Actually, this region is characterized by high photochemistry, above all during summer season, and by intense VOC biogenic and anthropogenic emissions implying the formation of SOA in the atmosphere. In this context, two field campaigns have been performed in the frame of Canopée and ChArMEx projects.Thanks to a sampling and analyzing method by TD-GC/MS, the characterization of organic fraction enables one to determine more than one hundred compounds from C2 to C18 in gaseous and particulate phases. In combination with traditional datasets (PTR-MS, AMS), new insights were brought in reactivity of gaseous oxygenated compounds with OH radical, in chemical composition of organic material in particulate phase and about the contribution of various precursors to the capacity to form SOA. The determination of experimental and theoretical partitioning coefficients gives new information on SOA representation in models

Le recyclage des résidus organiques (RO) en agriculture pourrait permettre de limiter l’utilisation des ressources minérales de phosphore (P), à condition de déterminer leur efficacité pour fournir du P aux cultures. L’objectif de ce travail était donc d’étudier les mécanismes déterminant l’effet des RO apportés au sol sur la biodisponibilité du P pour la plante (phytodisponibilité). Ce travail a été basé sur cinq essais de terrain à La Réunion, fertilisés sur une décennie avec des fertilisants organiques ou minéraux, et sur des expérimentations d’incubations en conditions contrôlées et de cultures de plantes en pot. Le P inorganique (Pi) et organique (Po) disponible du sol a été déterminé par des extractions (eau, Olsen), la technique des diffusive gradients in thin films (DGT) et la dilution isotopique associée à des membranes échangeuses d’ions. La capacité de sorption en Pi des sols a été évaluée avec des courbes de sorption. Le P phytodisponible a été déterminé en mesurant le P prélevé par la plante. Dans les différents types de sol (andosol, andique cambisol, nitisol et arenosol), l’apport de RO a augmenté le Pi disponible relativement au Po, suggérant que la minéralisation du Po issu des RO n’est pas un facteur limitant la disponibilité du Pi. Les RO ont augmenté le Pi disponible principalement par l’augmentation du pH du sol et par conséquent la diminution de sa capacité de sorption de Pi. Le P phytodisponible a augmenté avec le Pi disponible du sol, mais a diminué avec l’augmentation du pH du sol. Au-delà de la dose de P, l’effet de l’apport de RO à long-terme sur la phytodisponibilité du P semble principalement contrôlé par l’évolution induite du pH du sol. / Application of organic residues (OR) on agricultural soils could reduce the use of mineral phosphorus (P) fertilizers, but this implies to determine the efficiency of OR to meet crop requirements. We thus aimed to study mechanisms determining the effects of OR on P bioavailability to plants (phytoavailability). Our work was based on five field trials with decadal organic or mineral fertilization located in Réunion island, and on incubations and plant growth experiments under controlled conditions. Available inorganic P (Pi) and organic P (Po) was determined using extractions (water, Olsen), the diffusive gradients in thin films technique (DGT) and the isotopic dilution associated to anion exchange membranes (EAEM). Phytoavailable P was determined as the plant P uptake. Soil Pi sorption capacity was determined using sorption curves. For all soil types studied (andosol, andic cambisol, nitisol, and arenosol), RO increased mainly available Pi and had few effects on available Po, which suggests that mineralization of Po applied with RO does not limit Pi availability. Application of RO increased available Pi mainly by increasing soil pH and consequently by decreasing soil Pi sorption capacity. Phytoavailable P increased with soil available Pi, but decreased with increasing soil pH. Our work suggests that except the dose of P applied, effect of RO on P phytoavailability depends mainly on soil pH changes induced.

Polar organic compounds (POCs) are chemicals with polar functional groups in their structure. The functional groups make the compounds hydrophilic and less prone to partition with biota. However, the knowledge of their fate is limited due to difficulties associated with their measurements. Although, the persistence of POCs in the environment is generally low, they are considered to be semi-persistent compounds due to their continuous introduction to the environment via wastewater. Studies have shown that complex mixtures of POCs of different classes may have synergistic toxic effects on biota at environmental concentration levels. Therefore, it is important to develop analytical methods in order to establish the occurrence and fate of POCs in aquatic environments. In Study I, a positive correlation between the sorption of a novel poly(ethylene-co-vinyl acetate-co-carbon monoxide) (PEVAC) material and the theoretical logarithmic dissociation partition coefficient (Log D) for seven POCs was observed. The PEVAC material showed an enhanced sorption of the POCs compared to the silicone material. Study II, demonstrated that the PEVAC sampler assess the freely dissolved concentration of POCs in aquatic environments. The results showed that the PEVAC polymer is an attractive alternative to silicone for mimicing the biological uptake of POCs in aquatic environments. Additionally, Study II showed that total extraction is appropriate for determination of the freely dissolved concentration of uncharged POCs with Log KOW < 2.67 in natural water. In study III, a novel bag-solid phase extraction (bag-SPE) technique was compared to a conventional SPE-technique. Despite that the extraction efficiencies for POCs in wastewater were lower using the bag-SPE method, the two methods showed similar detection limits due to the lower ion-suppression experienced with the bag-SPE. In study IV the bag-SPE method was further developed with the aim of lowering the detection limits for POCs. Detection limits (LOD) below 13 ng/L showed that the bag-SPE method was suitable for determination of POCs in surface sea water. / This research was financially supported by European Union (European Commission, FP6 Contract No. 003956) “Novel Methods for Integrated Risk Assessment of Cumulative Stressors in the Environment” (NoMiracle) and by the Swedish research council Formas.