Irrigation using reclaimed wastewater can introduce organic contaminants and dissolved organic matter (DOM) to soils. Sorption of three common organic wastewater contaminants to five soils of diverse organic matter composition was studied both before and after the removal of soil carbohydrate and peptide components using acid hydrolysis. Results suggest that these polar components may block organic contaminants from accessing higher affinity sorption sites in soil organic matter. The sorptive fractionation of DOM by three mineral soils was studied to assess the terrestrial fate of this complex environmental matrix. Carboxyl- and aromatic-containing moieties appear to preferentially and reversibly sorb to mineral soils. Conversely, carbohydrate and peptide components of DOM preferentially remain in the aqueous phase while aliphatic moieties were selectively retained only by a soil with high surface area. This thesis illustrates that reclaimed wastewater should be applied to soils cautiously as it may degrade soil and groundwater quality.

Irrigation using reclaimed wastewater can introduce organic contaminants and dissolved organic matter (DOM) to soils. Sorption of three common organic wastewater contaminants to five soils of diverse organic matter composition was studied both before and after the removal of soil carbohydrate and peptide components using acid hydrolysis. Results suggest that these polar components may block organic contaminants from accessing higher affinity sorption sites in soil organic matter. The sorptive fractionation of DOM by three mineral soils was studied to assess the terrestrial fate of this complex environmental matrix. Carboxyl- and aromatic-containing moieties appear to preferentially and reversibly sorb to mineral soils. Conversely, carbohydrate and peptide components of DOM preferentially remain in the aqueous phase while aliphatic moieties were selectively retained only by a soil with high surface area. This thesis illustrates that reclaimed wastewater should be applied to soils cautiously as it may degrade soil and groundwater quality.

Bottom sediments around the world store large amounts of legacy hydrophobic organic contaminants (HOCs), forming mixtures of unknown chemical composition. Primary emissions to the environment of many HOCs have been reduced as a consequence of regulation. However, HOCs may be released from the sediments to water and biota, and there is therefore a risk of negative effects on local ecosystems. The activity of benthic organisms can enhance the sediment-to-water flux of HOCs, a process called bioturbation. Few in situ assessments of the sediment-to-water flux are available in the scientific literature, and the effect of bioturbation on the sediment-to-water flux of HOCs has not been studied in the field. Thus, there is a need to improve in situ methods for direct determination of sediments as a source of HOCs to water, and thereby include the effect of bioturbation. In Paper I, a benthic flow-through chamber was developed for environmentally realistic in situ assessments of the sediment-to-water flux. In Paper II, the sediment-to-water flux of polycyclic aromatic hydrocarbons (PAHs) was assessed using the flow-through chamber at four sites on the Swedish Baltic Sea coast. The sediments at all four sites acted as sources of PAHs to water. In the same study, potential effects of bioturbation, with an increase of the sediment-to-water flux by up to one order of magnitude, were observed at sites with bioturbating organisms. In the past, assessing the toxicity of HOCs has been challenging due to difficulties in maintaining stable exposure concentrations of the test chemical. In Paper III, a passive dosing method, where the test chemical partitions from a polymer (silicone) to the aquatic exposure medium, was developed and tested for chronic exposure. A stable exposure concentration could be maintained, and the chronic toxicity to the sediment-dwelling harpacticoid Nitocra spinipes of chronic exposure to triclosan was assessed in a 6-week population development test. In Paper IV, a passive sampling and dosing method was developed and used to assess the toxicity of an environmental chemical mixture of bioavailable sediment-associated HOCs transferred from a contaminated sediment to the laboratory-based bioassay. The passive sampling and dosing method can be used to assess the toxicity of environmental mixtures of chemicals at environmentally realistic concentrations to which ecosystems are constantly exposed. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p>

No description available.

Photodegradation is a major degradation mechanism for many environmental contaminants, both in indoor environments as well as in outdoor environments, and many of the contaminants are persistent and toxic. However, there is a lack of knowledge about the exact degradation process for many of them. It is important to not only monitor and study environmental contaminants that are commonly found. But it is also important to be able to identify their degradation products, however, due to lack of standards there is a difficulty to conduct identification. There is also the drawback with most spectral libraries used for identification being recorded at low resolution, when new instruments are being developed for using high resolution. This makes it challenging to identify compounds with spectral peaks that differ only slightly in their mass-to-charge ratio (m/z). Thus, the aim of this study was to determine potential degradation products from different compounds commonly found in indoor environments and then add these findings to a spectral library for high resolution mass spectrometry. This was conducted by first exposing the standards to ultraviolet (UV) light, and then the chemical analysis was performed using a gas chromatography coupled with a high resolution mass spectrometer. All data was then processed in different software in order to determine potential products. Many of the compounds did not indicate any degradation using the experimental settings, and for some not even the parent compound could be identified. In total, four potential degradation products were found in this study; degradation products were identified for hexabromobenzene (HBB) with penta-, tetra-, and tribromobenzene, as well as one potential product for 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB).

No description available.

No description available.

Although wastewater treatment plants are a line of defense in minimizing indiscriminate output of microconstituents to natural waters, we do not possess a fundamental understanding of the mechanisms involved in microconstituent removal during wastewater treatment. With this in mind, experiments were designed to investigate the factors that can influence the fate of four microconstituents, carbamazepine (CBZ), 17alpha-ethinylestradiol (EE2), iopromide (IOP), and trimethoprim (TMP), during biological suspended culture treatment. Specifically, the role that various ecological members of biological treatment systems play in biotransforming these compounds was evaluated. Sorption assays were performed with inactivated biomass samples (ammonia oxidizing bacteria (AOB), laboratory enriched heterotrophic cultures free of active nitrifiers with low (Ox⁻) or high (Ox⁺) oxygenase activity, and a nitrifying activated sludge (NAS) from a full-scale wastewater treatment plant) to determine whether partitioning dictates removal of individual microconstituents. No microconstituents sorbed to the AOB culture. Neither CBZ nor IOP sorbed to Ox⁻, Ox⁺ and NAS cultures; however, EE2 and TMP sorbed to the Ox⁻, Ox⁺ and NAS biomass. Sorption was positively influenced by the presence of exopolymeric substances (EPS) associated with the cultures. The protein content of EPS affected EE2 and TMP sorption more appreciably than the polysaccharide content of EPS. Further experiments were performed to investigate microconstituent biodegradation by AOBs, Ox⁻ and Ox⁺ cultures. The influence of growth state and oxygenase activity on biotransformation by each culture was also evaluated. Results indicate that EE2 was the only microconstituent that was amenable to biotransformation by batch cultured AOB and heterotrophic cultures. EE2 was biotransformed but not mineralized by AOB chemostat and batch cultures. TMP was not transformed by AOB batch or chemostat cultures; however both EE2 and TMP were transformed by Ox⁻ and Ox⁺ chemostat cultures. Radiolabeled studies showed that EE2 was mineralized by this culture. Kinetically, AOBs dominated EE2 transformation to monohydroxylated metabolites; however, both Ox⁻ and Ox⁺ cultures further degraded and mineralized EE2 and metabolites generated by AOBs. These results indicate that biotransformation of EE2 by NAS may be limited by heterotrophic activity whereas TMP fate may be a function of heterotrophic activity only. Oxygenase activity did not limit EE2 or TMP biotransformation in chemostat cultures. Subsequent experiments that were performed to identify the factors that influence heterotrophic degradation of EE2 and TMP indicated that the presence of readily biodegradable substrates slows EE2 and TMP biotransformation. The impact of slowly biodegradable substrates like EPS on EE2 and TMP degradation was unclear. These results suggest that EE2 and TMP are most amenable to biodegradation in bioreactors where endogenous conditions dominate. / Ph. D.

De nombreuses familles de polluants organiques en provenance de différentes sources se retrouvent dans les milieux aquatiques continentaux et littoraux. Ces molécules, dont les lipophiles et les persistantes, sont souvent présentes à l'état de trace dans la fraction dissoute. L'utilisation de compartiments concentrateurs comme les sédiments rend alors plus accessible l'évaluation des concentrations ambiantes du milieu. L'objectif de la thèse a été d'évaluer l'exposition en zones côtières aux différentes familles de contaminants organiques « émergents » incluant les filtres UV, les alkylphénols et les alkylphénols polyéthoxylés, ainsi que « persistants-classiques » incluant les hydrocarbures aromatiques polycycliques et les polychlorobiphényles dans les sédiments et, éventuellement, dans les eaux. Un important effort de recherche a été accordé à l'étude des variations spatiales et temporelles des contaminants sélectionnés dans les sédiments, permettant ainsi l'acquisition d'un premier jeu de données nationales (libanais) représentatif pour ces familles de contaminants.Trois rivières en Méditerranée orientale et leur environnement côtier ont été pris comme cas d'étude en plus de la côte d'une petite ville et ses sites portuaires qui ont été sélectionnés afin de compléter l'étude en milieu côtier. Un premier aperçu des niveaux de ces contaminants hydrophobes dans les zones côtières recevant des apports typiques de la Méditerranée orientale est ainsi fourni. Les résultats des analyses chimiques ont clairement montré l'impact des rejets des effluents non traités dans les zones côtières via les entrées des rivières et les déversements directs le long de la côte, en absence des activités récréatives (pour les filtres UV) et de rejets industriels (pour les alkylphénols et les alkylphénols polyéthoxylés). Les zones de transition peuvent être à l'origine de la contamination de l'environnement côtier des trois rivières par ces polluants émergents en absence des apports marins. Des concentrations élevées en hydrocarbures aromatiques polycycliques et en polychlorobiphényles ont été mesurées dans les sédiments prélevés en milieu côtier. Cette contamination a persisté des années après la marée noire qui a envahi la côte Est-Méditerranéenne en 2006. Nos résultats globaux indiquent que les concentrations mesurées dans les sédiments des trois rivières étudiées et du littoral peuvent être classées parmi les niveaux les plus élevés détectés dans le pourtour du bassin méditerranéen et pouvant induire des effets toxiques chez le biota aquatique.Ce travail peut être d'une importance primordiale pour la région Est-Méditerranéenne, et plus particulièrement pour le Liban, un pays qui, malgré d'être parmi les signataires de la convention de Barcelone pour la protection de la mer Méditerranée et qui est, par la suite, impliqué dans la surveillance de la qualité de son milieu marin, souffre jusqu'à présent des rejets de différents types d'effluents non traités le long de ces côtes en absence des stations d'épuration. / Many organic pollutants issued from different sources are present into freshwater and coastal waters. Since these lipophilic contaminants are present at trace levels in water, accumulator compartments such as sediments can be used to assess their concentration in aquatic systems. The objective of the thesis was to assess the exposure in coastal areas to the various families of organic contaminants namely "emerging pollutants" including UV filters, alkylphenols, alkylphenol polyethoxylates, and "persistent pollutants" including polycyclic aromatic hydrocarbons and polychlorinated biphenyls in sediments and water. A major research effort has been given to the investigation spatial and temporal dynamics of the selected pollutants in sediment, allowing the acquisition of a first set of national data (Lebanese).Three rivers and their coastal environment in the eastern Mediterranean have been taken as a case study in addition to the small coastal city that was selected to complete the study in the coastal environment. A first overview of the levels of these hydrophobic contaminants in coastal areas receiving typical eastern Mediterranean inputs is thus provided. The results of chemical analyzes have clearly shown the impact of discharges of untreated effluents into coastal areas via inputs from rivers and direct discharges along the coast, without recreational activities (for UV filters) and industrial effluents discharges (for alkylphenols and alkylphenol polyethoxylates). Transition zones may act like a source of contamination of the three rivers coastal environment in the absence of marine inputs. Elevated concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls were measured in sediments in coastal environments. This contamination has persisted for years after the oil spill that has invaded the Mediterranean coast in 2006. Our overall results indicate that concentrations in sediments of the three studied rivers and the coastline can be classified among the highest levels detected in the Mediterranean basin and may induce toxic effects in aquatic biota.This work may be of paramount importance for the East-Mediterranean region, and particularly for Lebanon, a country which, despite being a signatory to the Barcelona Convention for the Protection of the Mediterranean Sea and is, subsequently involved in monitoring the quality of its marine environment, suffers far different types of discharges of untreated effluent along its coast in the absence of wastewater treatment plants.

Contaminated land is a widespread, global issue affecting millions of people. Atrazine is a commonly used herbicide which often contaminates groundwater and drinking water supplies and is associated with adverse health outcomes. Biochar is the solid product of pyrolysis and is associated with several environmental benefits. It may be an effective remediation tool when used as a soil amendment. This thesis investigates the mechanisms through which biochar can immobilise atrazine, and the implications of the mechanisms for remediating contaminated land. Nine biochar samples were obtained from the United Kingdom Biochar Research Centre , which were produced from softwood pellets (SWP), wheat straw pellets (WSP), miscanthus straw pellets (MSP), rice husk (RH) and oil seed rape (OSR) each at pyrolysis temperatures of 550°C and 700°C (excluding OSR at 700°C). The sorption mechanisms controlling atrazine sorption to these biochars were determined through various characterisation methods and batch sorption experiments. The sorption tests showed that sorption to each of the standard biochars occurs via multiple simultaneously occurring mechanisms, which are each promoted under certain conditions. Studies investigating sorption kinetics, isotherms and interactions with humic acids showed that for all biochars in this study, pore filling was a significant process through which atrazine is transported to adsorption sites, although poor intraparticle diffusion for softwood and oil seed rape biochars can prevent efficient transport. Wheat straw and rice husk biochars showed effective pore diffusion, resulting in high sorption capacities. Partitioning was associated with poor remediation outcomes and was significant to softwood biochars, although adsorption dominated overall sorption for all other biochars. pH was shown to significantly influence the occurrence of various sorption mechanisms. At low pH values, most biochars showed evidence of electrostatic repulsion between positive atrazine species and the positively charged biochar surface. At intermediate pH values, all biochars showed strong hydrogen bonding between H+ groups on the surface of the biochar and atrazine. A meta-analysis of previous relevant studies provided further evidence for hydrogen bonding of atrazine to biochar and showed that hydrophobic effects likely play little role in adsorption after accounting for the effects of surface area. Varying contributions of π-π EDA interactions, hydrogen bonding involving biochar O- groups, and interactions with ash minerals resulted in different sorption profiles for each biochar at high pH values. In order to further determine the mechanisms controlling sorption at high pH, surface compositions of SWP550, RH700 and OSR550 biochars were modified using hydrofluoric acid. Modification with hydrofluoric acid successfully removed the ash contents of rice husk and oil seed rape biochars and reduced atrazine removal at high pH values. This suggested that the ash fraction increases atrazine removal at high pH through complexation or catalytic hydrolysis. The roles of the various mechanisms are related to remediation outcomes in a novel manner allowing for the improved design of biochar for environmental remediation.