Les PCB (polychlorobiphényles), PBDE (éthers de biphényles polybromés) et OCP (pesticides organochlorés) sont des composés d’origine anthropique classés comme POP (polluants organiques persistants) dont l’usage a progressivement été restreint ou interdit. Ces composés, de par leur caractère ubiquiste, persistant et bioaccumulable, sont néanmoins toujours présents dans l’environnement, d’où l’importance de continuer à étudier leur présence, leur dynamique et leur impact. Du fait de la restriction de leurs usages, d’autres composés sont maintenant utilisés pour les remplacer, tels que les retardateurs de flamme alternatifs (RFA). Ces composés bromés et chlorés ont des propriétés physico-chimiques comparables à celles des POP précités et peuvent potentiellement constituer un danger chimique pour l’environnement. Par ailleurs, les RFA sont attendus à des niveaux de concentration plus faibles que les PCB et les PBDE que ce soit dans les compartiments biotiques et abiotiques. Ainsi, l’un des enjeux de ce travail de thèse était de développer une méthode multi-résidus, associant chromatographie en phase gazeuse et spectrométrie de masse à temps de vol, permettant d’analyser simultanément 17 RFA à des niveaux inférieurs au ng.g-1. Les niveaux et profils de contamination en POP et RFA ont ensuite été renseignés dans les compartiments biotiques et abiotiques de différents systèmes aquatiques contrastés. Le caractère bioamplifiable de ces composés a été étudié grâce à la détermination de facteurs d’amplification trophique (TMF) dans l’estuaire de la Gironde et dans le bassin du Rhône, à l’aide d’outils statistiques innovants. Dans l’estuaire de la Gironde il a été mis en évidence que certains RFA étaient autant voire plus bioamplifiables que certains POP historiques. Par ailleurs, dans le bassin du Rhône, l’utilisation des TMF comme outil prédictif, pour le BDE-47 ou la ΣPBDE-DCE par exemple, a été discutée et parait envisageable dans un cadre réglementaire. / PCBs (polychlorinated biphenyls), PBDEs (polybrominated biphenyl ethers) and OCPs (organochlorine pesticides) are anthropogenic compounds classified as POPs (Persistent Organic Pollutants), their use was restricted or prohibited. These compounds are ubiquitous, persistent and bioaccumulative and they are still present in the environment; this is the reason why it is important to continue the study of the fate and impact in the environment. Due to their usage restriction, other compounds are now used to replace them, such as alternative flame retardants (RFAs). These brominated and chlorinated compounds have physicochemical properties comparable to those of POPs and can thus be potentially hazardous to the environment. In addition, RFAs are expected to occur at lower concentrations than PCBs and PBDEs, whether in the biotic and abiotic compartments. Thus, one of the challenges of the present work was to develop a multiresidue method, based on gas chromatography coupled with a time-of-flight mass spectrometer, allowing for the simultaneous analysis of 17 RFAs at levels below ng.g-1. The levels and patterns of POP and RFA contamination were reported in the biotic and abiotic compartments of selected hydrosystems. The biomagnification potential of these compounds was also studied by determining trophic magnification factors (TMF) in the Gironde estuary and in the Rhône basin. In the Gironde estuary, it was shown that some RFA biomagnify as much or more than some historical POPs. Furthermore, in the Rhône basin, the use of TMF for predictive purpose, for BDE-47 or ΣPBDEs-WFD for example, was discussed and found possible.

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The use of treated wastewater (TWW) for crop irrigation is how many governments are looking to feed their large population due to urbanisation. Here, we outline and analyse the benefits of using TWW and the drawbacks of such practices in line with existing regulations. The review begins by highlighting the history of wastewater reuse in agriculture. The approach used in the write-up is outlined after the background. There is an in-depth look at three main areas: the uptake of heavy metals and pharmaceuticals on crop irrigation, plant yield, and the impact of regulations on these practices. Results demonstrate the presence of several pharmaceuticals, triclosan, acetaminophen, diazepam in lettuce, meprobamate, atenolol in celery, and carbamazepine, triclosan, and triclocarbon in soybean. Trace metals (Cd, Pb) are present in the edible part of the vegetable and arsenic is found in the ryegrass roots and maise. Some benefits derived from using TWW in crop irrigation include nutrient supply, water resource protection and food security, whereas the drawbacks are exposure of contaminants to food and humans.

Bioretention is increasingly being employed as a stormwater management tool in urban areas, with the intent of using infiltration to address both water quantity and quality concerns. However, bioretention soil media (BSM) has limited removal capacity for dissolved contaminants; hence, amendments may be justified to improve performance. In this study, the potential of five low-cost sorbents as BSM amendments – waste tire crumb rubber (WTCR), coconut coir fiber (CCF), blast furnace slag (BFS), biochar (BC) and iron coated biochar (FeBC) – were investigated for removing several classes of contaminants from simulated stormwater (SSW). The contaminated SSW contained a mixture of metals (Cr, Cd, Cu, Pb, Ni and Zn), nutrients (ammonium, nitrate, and phosphate) and PAHs (pyrene (PYR), phenanthrene (PHE), acenaphthylene (ACY) and naphthalene (NAP)). First, batch studies were used to investigate the sorption capacities, kinetics, and the effects of different water quality parameters on sorbents performance. Then, a long-term vegetated column study was conducted to investigate the performance of three amendments (CCF, WTCR, and BFS) under intermittent runoff condition considering different runoff intensities and antecedent dry periods (ADP). The long-term effects of amendments on plant health and infiltration rate of all media were also investigated. Finally, HYDRUS-1D and a cost model were used to investigate longevity and cost-effectiveness of all BSM. Batch test results revealed that among all sorbents, BC and FeBC were only effective for removing PAHs; CFF had high sorption capacity for both metals and PAHs; BFS was very effective for metals; and WTCR was effective for some of metals and PAHs. Metal removal by BFS occurred primarily via precipitation was due to the BFS mineral structure and high/alkaline pH. The effectiveness of CCF for removing both metals and PAHs was due to its lignocellulose structure and diverse functional groups. CCF could remove metals through several mechanisms including cation exchange, complexation, and electrostatic attraction, and remove PAHs through hydrophobic interaction. Biochar in this study had a highly aromatic structure with less O-containing functional groups, and PAHs were sorbed through hydrophobic pi-pi interactions. The selectivity orders of sorbents for the removal of different metals and PAHs were Cr~Cu~Pb > Ni > Cd > Zn and PYR > PHE > ACY > NAP. This selectivity was mainly caused by differences in properties of metal ions (e.g., ionic radius, hydrogen energy, etc.) and PAHs (e.g., hydrophobicity). Phosphate was removed by BFS due to its Al, Fe and Ca contents, but the other sorbents were ineffective for nutrient removal. Metals sorption capacity of sorbents was greater at higher pH, lower salinity and lower DOC; however, PAHs sorption capacity of sorbents was generally not sensitive to water quality parameters. Column experiments showed that almost all amended and non-amended BSM were able to remove > 99% of influent metals over the 7-month experiment period (except Zn in WTCR media). Cu and Cr effluent concentrations in all media (except BFS media) increased to ~ 10% of influent concentrations during heavy rainfall which was probably due to decomposition of Cu/Cr-organic matter complexes. All bioretention columns removed > 99% of PHE and PYR (higher molecular weight PAHs) regardless of rain intensity and ADP, while the performance of different media for removing the lower molecular weight PAHs (NAP and ACY) varied with the rain intensity, and removal decreased when larger storms were experimentally simulated. For nutrients, among all media, BFS-amended media had high phosphate removal capacity (> 90%). Nitrate removal in all columns was notably affected by changes in stormwater intensity and ADP, likely due to difference in degree of saturation and the potential that anoxic conditions were created, which are favorable for denitrification. All media were ineffective in ammonium removal, and ammonium production occurred throughout experiment which might be due to the lack of nitrifiers in the media. Hydraulic properties of all media were appropriate over the entire experiment. BFS-amended media had the greatest negative effect on plant health, while CCF-amended media was supportive for plants. The transport model results showed that the predicted metal breakthrough times (according to EPA criteria) for different media were 6 years for non-amended media, 7 years for WTCR media, 25 years for CCF media, and 70 years for BFS media. Modeling PAHs, nutrients and some metals (Cr and Cu) under intermittent flow conditions are complicated and other processes and models need to be investigated as future study. Finally, cost analysis results showed that among all bioretention media, CCF- and BFS-amended media with the lowest capital and maintenance costs were the most cost-effective BSM. This research will improve our understanding of BSM amendments that will improve water quality while simultaneously support bioretention system hydrologic function as well as estimating costs of bioretention systems for a long-term application. / Civil Engineering

There are a great variety of environmentals contaminants, a lot of which are understudied asit is today. The aim of this study was to develop an in-house high-resolution spectral librarycontaining environmental contaminants, with focus on plastic additives. The spectral librarywould then be used to perform suspect screening on real sample extracts. A list of standardswas acquired, prepared and then analyzed with GC-EI-Orbitrap. The files from the analysiswere converted and then processed in a software called MS-DIAL. Once the analyte wasidentified, the data was exported to MS-FINDER. MS-FINDER performs fragmentannotation and generates in silico spectra, and the spectral data is then saved as an MSP file.An MSP file is a file based on text containing mass spectrometric data, and is the mostcommonly supported file for spectral libraries. The individual MSP files for the standards arethen collected into a common MSP file, which can be opened in MS-DIAL to performsuspect screening. The suspect screening in this study was performed as a retrospectiveanalysis of indoor dust samples from a study in 2021.From the beginning, 60 standards out of 80 available standards were included. The principalreason for a standard not being included was that the compound would most certainly notelute using GC with the set analytical parameters. Out of the 60 analyzed standards, 32compounds could be added to the spectral library. No distinct peak within thechromatographic run time was the main reason for not being able to add a standard. Despiteadding 32 different compounds into the spectral library, a total of 51 individual MSP-fileswere generated. Some of the technical mixtures generated a chromatogram with severaldifferent peaks, and MSP files were generated for each of the most prominent peaks. Thiswas done since it could still provide useful information in an identification process.The suspect screening in this study was performed as a retrospective analysis of indoor dustsamples from 2019. Into the spectral library, 32 different compounds were included, and 10of these were found in the different indoor dust samples when performing the suspectscreening.Building a spectral library in this way is a time consuming process with a lot of manual work,but spectral libraries are nonetheless necessary in the process of effectively monitoringenvironmental contaminants, to assist in risk assessment and decision making for regulatorson identified contaminants.

In this study I assess spatial and temporal patterns of sediment deposition in Pecausett Pond, located along the tidal extent of the Connecticut River, in order to assess the role of tides in the transport and storage of sediment and associated contaminants within floodplain tidal ponds. Findings reveal that tidal ponds have significantly higher rates of sedimentation compared to neighboring marshes due to the fact that these ponds have more accommodation space and receive uninterrupted tidal exchange with the main river. Tidal tie channels introduce a pulse of suspended sediment and contaminants from the main river into these ponds each flood tide, with sedimentation rates fast enough to allow settling before the subsequent ebb tide can transport these sediments back to the main river (i.e. tidal pumping). Some studies performed on the tidal floodplain of the Connecticut River show high deposition rates and have attributed periods of high accumulation to anomalously high river discharge events. However, this project shows that tides are more likely the major mechanism responsible for transporting and storing sediment and associated contaminants at backwater sites located along the tidal floodplain. Deposition rates in this 3-4 m deep pond exceed 2 cm/yr. These rates are far too high to maintain equilibrium morphology for much longer. However, ground penetrating radar surveys from the study site reveal truncated stratigraphy common to erosional unconformities, which suggest that mechanisms for sediment remobilization and removal may exist. Periods of episodic erosion therefore may be helping to maintain the morphology in this shallow environment, and allow for the high rates of short-term deposition. Further, a sudden increase in percent inorganic potentially associated with the opening or clearance of the tie-channel is observed at a sediment depth approximately between 1.9 to 2.2 m. A radiocarbon date obtained below this transition is consistent with a significant drop in sedimentation prior to this tie-channel development. High rates of sedimentation in Pecausett Pond are therefore likely relatively recent phenomena, transpiring over the last few centuries following early colonization.

Current models for predicting the environmental fate of munitions constituents (MC) in soils are based mostly on chemical distribution parameters and neglect the larger considerations of other soil parameters. We are working towards a new approach based on the whole soil activity for predicting the long-term residence time and fate of MC in soils with connection to agronomic soil fertility concepts. These relationships are demonstrated by correlating experiments involving full physical and chemical characterization of eight taxonomically distinct soils, with batch reactor studies determining MC degradation potential. Soils were incubated in a slurry for 10 days in a closed reactor system with temperature, pH, and Eh readings recorded every 24 h. Air and slurry samples were taken eight times within the 168 h incubation period. Carbon dioxide, TNT, and nutrient solution concentrations were assessed to obtain a full picture of soil chemistry changes associated with microbial activity in response to additions of TNT. Multivariate analysis was used to determine the main factors impacting degradation rate. Principle Components Analysis (PCA) statistically classified the soils based on the variance of their soil property data. Partial Least Squares Analysis (PLS) showed that TNT degradation was possibly correlated with soil fertility characteristics. Although this is an exploratory study, results show promise in moving towards a more effective way of predicting TNT environmental fate in soils.

Aluminium has great properties that are utilised the world over, but the production of primary aluminium is very energy intensive. In order to reduce the energy-cost, the aluminium can be recycled by re-melting aluminium scrap. This results in a circularity of the aluminium, as it is produced from ore to a metal and then the metal scrap can be re-melted again for other use.  The study also focuses on secondary production in Sweden. Through interviewing diverse actors in Sweden and analysing literature, an understanding of how the circulatory systems work was developed and the problems that can occur within it.  The major problems found is that through re-melting, the previous alloying elements can become impurities in the new scrap-based material. These impurities can change the properties in the aluminium. Separating these impurities from the aluminium is not an easy process, but a growing research question. Easiest is to minimise these contaminations, companies do this by sourcing where scrap is coming from and its compositional information, so to better organize or use the scrap for a similar purpose aluminium alloy.  This study looked at how the circulation of aluminium scrap works and how used scrap is once again returned to new reusable aluminium. With an understanding of how the processes it is easier to locate problems to improve the processes. / Aluminium har mycket goda mekaniska egenskaper som används i hela världen, men att producera primär aluminium är extremt energikrävande. För att minska energikostnaden kan man återvinna aluminiumet, det görs genom att återanvända gammalt aluminiumskrot. När man gör detta så leder det till ett cirkulärt kretslopp, där det börjar från malm som produceras till metall, när metallen blir till skrot så kan det återanvändas för att producera nytt aluminium.  Genom att intervjua folk inom branschen och att analysera litteratur inom ämnet, så skapades en förståelse hur det cirkulär kretsloppet fungerar och problem som kan uppstå inom systemet.  Det största problemet som hittades var att genom att återvinna aluminium skrot, så kan det tidigare legeringselement bli föroreningar i den nya skrot baserade materialet. Dessa föroreningarna kan ändra egenskaperna hos aluminiumet. För att får bort dessa föroreningar kan vara en svår process eller fortfarande utvecklande processen. Det är mycket lättare att försöka undvika dessa föroreningarnas från börja. Företagen gör detta genom att veta var skrotet kommer ifrån och skrotets legeringsämnen innan de återanvänder det. Då kan de organisera skrotet bättre och använda det till liknande skrot material i framtiden.  Denna studien fokuserar på hur skrotbaserat aluminium fungerar i ett kretslopp och hur gammalt skrot kan återanvändas till ny användbar aluminium. Med en förståelse på hur processen fungerar, så är det mycket lättare att hitta problem som kan leda till möjligheter att förbättra processen.

La diversité croissante dans l’environnement de composés potentiellement fœtotoxiques est une préoccupation de santé publique. L’objectif de ce travail était de contribuer à l’élaboration de méthodes rapides et efficaces pour en évaluer l’exposition prénatale. La modélisation de la relation quantitative structure à activité (QSAR) est apparue comme une méthode de choix dans l’élaboration d’un modèle prédictif pour le passage placentaire des contaminants. Les ratios fœto-maternels de concentrations sanguines pour 105 contaminants ont été compilés à partir de la littérature, et 214 descripteurs moléculaires ont été générés. Dix modèles prédictifs ont été élaborés à l’aide du logiciel Molecular Operating Environnement (MOE) et des langages de programmation Python et R. Les jeux de données d’entrainement et de test ont été utilisés, respectivement, pour élaborer et valider les modèles. L’outil Applicability Domain v1.0 a été utilisé pour déterminer le domaine d’applicabilité (DA). Les modèles élaborés avec les méthodes de régression des moindres carrés partiels dans MOE et SuperLearner dans R, ont montré les meilleures valeurs de précision et de prédictivité avec des coefficients de détermination internes (R2) de 0,88 et 0,82, des R2 de validation croisée de 0,72 et 0,57, et des R2 externes de 0,73 et 0,74, respectivement. Le recouvrement de toutes les molécules du jeu de test par le domaine d’applicabilité a permis de démontrer la fiabilité et la pertinence des prédictions des modèles. Les résultats obtenus démontrent que les modèles élaborés peuvent aider à quantifier l’exposition fœtale aux composés toxiques de l’environnement à partir des concentrations sanguines de la mère. / The increasing diversity of environmental chemicals in the environment, some of which may be developmental toxicants, is a public health concern. The aim of this work was to contribute to the development of rapid and effective methods to assess prenatal exposure. Quantitative structure-activity relationships (QSAR) modeling has emerged as a promising method in the development of a predictive model for the placental transfer of contaminants. Fetal to maternal plasma or serum concentration ratios for 105 chemicals were extracted from the literature, and 214 molecular descriptors were generated for each of these chemicals. Ten predictive models were built using Molecular Operating Environment (MOE) software, and the Python and R programming languages. Training and test datasets were used, respectively, to build and validate the models. The Applicability Domain Tool v1.0 was used to determine the applicability domain. The models developed with the partial least squares regression method in MOE and SuperLearner in R, showed the best precision and predictivity, with internal coefficients of determination (R2) of 0.88 and 0.82, cross-validated R2s of 0.72 and 0.57, and external R2s of 0.73 and 0.74, respectively. The inclusion of all test chemicals by the domain of applicability demonstrated the reliability and relevance of the model predictions. The results obtained demonstrate that QSAR modeling can help quantify placental transfer of environmental chemicals.

La propolis est un produit de la ruche à base de résine de plantes et d’arbres mélangée à de la cire d’abeille. Elle est utilisée pour polir les murs de la ruche et la protéger contre les intrus provenant de l’extérieur. Elle contient un grand nombre de composés incluant les métabolites des plantes, alors elle est un ingrédient des médicaments naturels, des additifs alimentaires et des produits cosmétiques en raison de sa richesse en polyphénols qui lui confèrent ses propriétés anti-oxydantes, anti-inflammatoires et antibiotiques. La composition de la propolis est cependant complexe et très variable en raison de la région de provenance qui est étroitement liée aux résines utilisées par les abeilles. De plus, la présence de contaminants dans l’environnement, comme les pesticides et les éléments traces d’origine anthropique, incluant des métaux lourds, donne un risque d’exposition à ces substances en consommant la propolis ou les extraits de propolis. Plusieurs échantillons de propolis brute ainsi que des teintures commerciales et artisanales provenant du Canada, de la Roumanie et du Brésil ont été analysés. L’extraction des polyphénols totaux des échantillons bruts a été faite 3 fois dans l’éthanol (EtOH) 70 % (v/v) à 70 ̊C, et les teintures ont quant à elles été diluées dans l’EtOH 70 %. Les polyphénols totaux ont ensuite été analysés par spectroscopie moléculaire UV-Vis en utilisant la méthode de Folin- Ciocalteu. Des analyses chromatographiques préliminaires par la chromatographie liquide couplée à la spectrométrie de masse (LC-MS) ont permis de comparer des polyphénols et des pesticides dans deux sources de propolis du Québec, avec une grande similarité entre les deux extraits. Des échantillons bruts ainsi que des extraits éthanoliques et des teintures ont été analysés suite à l’ionisation par plasma à couplage inductif (ICP-MS) et la spectroscopie de fluorescence atomique à vapeur froide (CVAFS) pour déterminer des concentrations de certains éléments traces présents à l’état de trace incluant l’As, le Cd, le Pb et le Hg total. / Propolis is a honeybee product made of plant and tree resins mixed with beeswax. It is used to build and repair the walls of the hive and to protect it from outside invaders. It contains a large number of compounds including plant metabolites, and is thus used in natural medications, cosmetic products and as food additives due to its richness in polyphenols, which confer its antioxidant, anti-inflammatory and antibiotic properties. However, the composition of propolis is complex and highly variable because of the geographical location of the resins used by the bees. Furthermore, the presence of contaminants in the environment, such as pesticides and trace elements of anthropogenic origin, brings a risk of exposure to these substances when consuming the propolis. Various raw propolis samples as well as commercial and homemade tinctures from Canada, Romania and Brazil were analysed. The raw samples were extracted 3 times in 70 % EtOH (v/v) at 70 ̊C, whereas the tinctures were diluted in 70 % EtOH. The total polyphenol content was determined by UV-Vis spectroscopy using the Folin-Ciocalteu method. Preliminary chromatography analyses by LC-MS on two propolis samples from Québec showed that the detected polyphenols and pesticides in their extracts were very similar, with only a few compounds found exclusively in either one or the other sample. Several raw propolis samples, their extracts and some tinctures were analyzed by ICP-MS and CVAFS to determine trace concentrations of heavy metals including As, Cd, Pb and total Hg.