Abstract The releases of chlorinated volatile organic compounds (CVOCs) are controlled by strict regulations setting high demands for the abatement systems. Low temperature catalytic oxidation is a viable technology to economically destroy these often refractory emissions. Catalysts applied in the oxidation of CVOCs should be highly active and selective but also maintain a high resistance towards deactivation. In this study, a total of 33 different γ-Al2O3 containing metallic monoliths were studied in dichloromethane (DCM) and 25 of them in perchloroethylene (PCE) oxidation. The active compounds used were Pt, Pd, Rh or V2O5 alone or as mixtures. The catalysts were divided into three different testing sets: industrial, CVOC and research catalysts. ICP-OES, physisorption, chemisorption, XRD, UV-vis DRS, isotopic oxygen exchange, IC, NH3-TPD, H2-TPR and FESEM-EDS were used to characterise the catalysts. Screening of the industrial catalysts revealed that the addition of V2O5 improved the performance of the catalyst. DCM abatement was easily affected by the addition of VOC or water, but the effect on the PCE oxidation was only minor. Based on these screening tests, a set of CVOC catalysts were developed and installed into an industrial incinerator. The comparison between the laboratory and industrial scale studies showed that DCM oxidation in an industrial incinerator could be predicted relatively well. Instead, PCE was always seen to be oxidised far better in an industrial unit indicating that the transient oxidation conditions are beneficial for the PCE oxidation. Before starting the experiments with research catalysts, the water feed was optimised to 1.5 wt.%. Besides enhancing the HCl yields, water improved the DCM and PCE conversions. In the absence of oxygen, i.e. during destructive adsorption, the presence of water was seen to have an even more pronounced effect on the HCl formation and on the catalysts’ stability. In the DCM oxidation, the addition of the active compound on the catalyst support improved the selectivity, while the enhancing effect on the DCM conversion was only small. The high acidity together with the increased reducibility was seen to lead to an active catalyst. Among the research catalysts Pt/Al2O3 was the most active in the DCM oxidation. With PCE the addition of the active compound proved to be very beneficial also for the PCE conversion. Now Pt and Pd supported on Al2O3-CeO2 were the most active. The enhanced reducibility was seen to be the key feature of the catalyst in PCE oxidation. / Tiivistelmä Klooratuille orgaanisille hiilivedyille (CVOC) on asetettu tiukat päästörajoitukset niiden haitallisten vaikutusten takia. Tästä johtuen myös puhdistusmenetelmien tulee olla tehokkaita. Katalyyttinen puhdistus on teknologia, jolla nämä usein vaikeasti käsiteltävät yhdisteet voidaan taloudellisesti tuhota. Käytettävien katalyyttien tulee olla aktiivisia ja selektiivisiä sekä hyvin kestäviä. Tässä työssä tutkittiin yhteensä 33 erilaista γ-Al2O3-pohjaista hapetuskatalyyttiä metyleenikloridin (DCM) käsittelyssä, niistä 25 testattiin myös perkloorietyleenin (PCE) hapetuksessa. Aktiivisina metalleina katalyyteissä käytettiin platinaa, palladiumia, rhodiumia ja vanadiinia yksin tai seoksina. Katalyytit jaettiin kolmeen ryhmään: teolliset-, CVOC- ja tutkimuskatalyytit. Aktiivisuuskokeiden lisäksi katalyyttejä karakterisoitiin ICP-OES-, fysiorptio-, kemisorptio-, XRD-, UV-vis DRS-, isotooppivaihto-, IC-, NH3-TPD-, H2-TPR- ja FESEM-EDS-pintatutkimusmenetelmillä. Koetulokset osoittivat, että vanadiini paransi teollisuuskatalyyttien aktiivisuutta ja selektiivisyyttä. VOC-yhdisteen tai veden lisäys paransi DCM:n hapettumista, mutta PCE:n hapettumiseen niillä ei ollut vaikutusta. Testien perusteella kehitettiin CVOC-katalyytit, jotka asennettiin teolliseen polttolaitokseen. Laboratoriossa ja teollisuudessa tehdyissä testeissä havaittiin, että DCM:n hapettuminen oli laboratoriokokeiden perusteella ennustettavissa. Sen sijaan PCE hapettui teollisuudessa aina paljon paremmin kuin laboratorio-olosuhteissa. Tämä osoittaa, että muuttuvat hapettumisolosuhteet vaikuttivat positiivisesti PCE:n hapettumiseen. Veden määrä syöttövirrassa optimoitiin 1,5 %:iin ennen tutkimuskatalyyttien testausta. Selektiivisyyden lisäksi vesi paransi DCM:n ja PCE:n konversiota. Hapettomissa olosuhteissa, ts. tuhoavien adsorptiokokeiden aikana, vesi paransi reaktion selektiivisyyttä HCl:ksi ja CO2:ksi vielä entisestään. Tämän lisäksi vesi lisäsi katalyytin stabiilisuutta. DCM:n hapetuksessa aktiivisen metallin lisäys paransi selektiivisyyttä, mutta sen sijaan vaikutus DCM:n konversioon oli hyvin pieni. Tulokset osoittivat, että aktiivisella DCM:n hapetuskatalyytillä tulee olla korkea happamuus ja hyvä pelkistyvyys. Pt/Al2O3 oli testatuista tutkimuskatalyyteistä aktiivisin. PCE:n hapetuksessa aktiivisen metallin lisäys paransi selektiivisyyden lisäksi huomattavasti myös konversiota. Katalyytin lisääntyneen pelkistymiskyvyn todettiin olevan keskeisin ominaisuus PCE:n hapettumisessa. Pt/Al2O3-CeO2 ja Pd/Al2O3-CeO2 olivat tutkimuskatalyyteistä aktiivisimpia.

Detta examensarbete syftade till att undersöka om lera kan förhindra en spridning av klorerade lösningsmedel ned till grundvattnet samt vid vilka hydrogeologiska förhållanden som lera har störst potential att vara tätande. Det övergripande målet med arbetet var dock att bidra till att tydliggöra definitionen av och förbättra kunskapsläget om tätande jordlager på Sveriges Geologiska Undersökning (SGU). Sju förorenade områden där klorerade lösningsmedel påvisats i jord och/eller grundvatten valdes ut till en jämförande fallstudie. Samtliga områden var belägna inom 750 m från något av SGUs lokalkarterade grundvattenmagasin och lera överlagrade helt eller delvis grundvattenmagasinet på platsen. Resultatdata i form av jord- och grundvattenprov från tidigare undersökningar av områdena lagrades in i databaser på SGU. Spridningen av klorerade lösningsmedel på varje område analyserades sedan genom att titta på var i området olika koncentrationer uppmätts och hur koncentrationerna förändrats med djupet. Spridningen jämfördes även med lerförekomsten på varje område både med avseende på lermäktighet och på placeringen av leran i området. Områdena jämfördes sedan med varandra för att se om det fanns ett samband mellan lerförekomst och spridningsbild samt för att tydliggöra hur förhållandena på platsen bör se ut för att ett lerlager ska vara tätande. Resultaten stämmer väl överens med de tidigare studier som visat att lera kan ha en uppbromsande effekt vid spridningen av klorerade lösningsmedel. Däremot kan lera inte sägas vara tätande utan att tidsaspekten tas med i definitionen. Även storleken på utsläppet har betydelse för hur länge ett lerlager kan hålla tillbaka spridningen. Studien tyder också på att så kallade svallsediment kan öka jordlagrens potential att vara tätande genom att bromsa upp och sedan avleda den vertikala spridningen av klorerade lösningsmedel samt att lera har en större potential att vara tätande ifall lerlagret är beläget några meter ned i jorden och leran är vattenmättad. Det är däremot svårt att dra några slutsatser kring vilken mäktighet ett lerlager måste ha för att vara tätande. Endast i ett av de utvalda områdena hade det undre grundvattnet skyddats mot spridningen av klorerade lösningsmedel förmodligen tack vare en kombination av ett mycket mäktigt lerlager, ett övre grundvattenmagasin i svallsedimentet och en uppåtgående strömning av grundvatten från det nedre till det övre grundvattenmagasinet. Slutligen visar examensarbetet att i områden med punktutsläpp av klorerade lösningsmedel har de lokala förutsättningarna för stor påverkan för att en viss lermäktighet ska kunna sägas vara tätande och försiktighet bör tas vid användning av begreppet tätande jordlager i generella sammanhang.

L'exposition humaine au bisphénol A et aux nonylphénols constitue un problème majeur de santé publique, en conséquence du caractère ubiquitaire de ces molécules et de leur toxicité en tant que perturbateur endocrinien. Leurs dérivés chlorés, formés par chloration lors de l'étape de désinfection de l'eau potable, présentent un effet perturbateur endocrinien jusqu'à 100 fois plus important que les composés parents. Au cours de ce travail nous avons développé des méthodes de dosage sensibles et reproductibles par LC-MS/MS de ces polluants dans l'eau. Le choix de l'isomère 353NP a été discuté et retenu comme substance de référence des nonylphénols. Le bisphénol A et le 353NP ont été retrouvés dans l'eau de surface (en entrée) et dans l'eau traitée (en sortie) de 8 usines de traitement d'eau potable, à des concentrations comprises entre 2,0 et 29,7 ng.L-1 et entre <4,1 et 124,9 ng.L-1 respectivement. Par ailleurs, aucun dérivé chloré n'a été détecté. Des dosages du bisphénol A et de ses dérivés chlorés réalisés dans 14 eaux du robinet et 4 eaux embouteillées ont montré leur présence dans ces eaux de boisson. Pour évaluer l'imprégnation de la population au bisphénol A et ses dérivés chlorés, nous avons mis au point un dosage ultrasensible de ces molécules par SPE-UPLC-MS/MS dans le lait maternel, validé selon les recommandations internationales. Ces composés ont été retrouvés dans le colostrum de 21 mères avec des concentrations comprises entre <0,40 et 6,12 ng.mL-1. Ces résultats prouvent qu'il existe une origine hydrique de la contamination chez l'homme par le bisphénol A, comme pour ses dérivés chlorés. / Bisphenol A and nonylphenols are widespread industrial chemicals which over the past decade have demonstrated their toxicity as endocrine disruptors. Residual chlorine present in drinking water may react with these compounds to form chlorinated derivatives, which have demonstrated a heightened level of estrogenic activity. In this work, we have comprehensively validated accurate and reproducible methods of quantification measuring these target compounds in water using LC-MS/MS. We have discussed and selected 353NP as the reference material for the analysis of nonylphenols. Bisphenol A and 353NP were found in both surface and treated water samples extracted from eight French drinking water treatment plants, at a level ranging from 2.0 to 29.7 ng.L-1 and from <4.1 to 124.9 ng.L-1, respectively. Neither chlorinated BPA nor chlorinated 353NP was detected. Quantification of bisphenol A and its chlorinated derivatives in 14 tap water samples and 4 bottled water samples showed that those pollutants are present in drinking water. Exposure to bisphenol A and its chlorinated derivatives in the population was investigated through breast milk. We developed a method using on-line SPE-UPLC-MS/MS to quantify these chemicals in breast milk according to internationally accepted guidelines. The target compounds were found in the colostrum of 21 women at concentrations ranging from <0.40 to 6.12 ng.mL-1. Drinking water may consequently constitute a source of human exposure to bisphenol A and its chlorinated derivatives.

Les conditions de sécurité sanitaire encadrant les pratiques d'hémodialyse (HD) et d'hémodiafiltration (HDF) n'intègrent pas les risques liés à des micropolluants comme les perturbateurs endocriniens (PE). Les patients dialysés présentent un risque de surexposition au Bisphénol A (BPA), reconnu comme PE, en raison de sa présence dans les dispositifs médicaux utilisés lors de la dialyse et du risque d'accumulation liée à leur état rénal.Nos premiers travaux ont confirmé la présence du BPA dans les dialyseurs et démontré pour la 1ère fois que l'eau utilisée en HD était également une source de contamination importante en BPA, via la production du dialysat. De plus, nous avons mis en évidence dans l'eau de dialyse la présence de dérivés chlorés du BPA (ClxBPA), sous-produits de chloration de l'eau connus pour leur activité œstrogénique supérieure au BPA. Nous avons ensuite montré que l'HDF entrainait un risque d'exposition aux PE plus important que l'HD, via la contamination du liquide de substitution perfusé chez le patient. Ces résultats permettront aux industriels de prendre en compte le risque de contamination à ces PE ainsi qu'aux médecins et pharmaciens impliqués dans la prise en charge des patients dialysés.Peu de données sont disponibles concernant l'impact clinique d'une telle exposition chez le patient dialysé et aucune étude n'a intégré le risque lié aux ClxBPA. C’est pourquoi, nous avons développé des biomarqueurs d'exposition en mettant au point des méthodes de dosage ultrasensibles du BPA et des ClxBPA dans les urines et le plasma. Ces biomarqueurs permettront d'étudier l'impact des différentes techniques de dialyse sur l'exposition des patients à ces PE. / The health safety conditions for the practice of hemodialysis (HD) and hemodiafiltration (HDF) do not integrate the risks associated with micropollutants such as endocrine disruptors (ED). Dialysed patients are at risk of overexposure to Bisphenol A (BPA), a well-recognized ED, due to its occurrence in medical devices used during dialysis and to the risk of accumulation due to their renal impairment.In a first step we have confirmed BPA contamination in dialyzers and demonstrated, for the first time, that the water used in HD was a significant source of BPA contamination, via dialysate production. Furthermore, we highlighted the presence of chlorinated derivatives of BPA (ClxBPA), by-products of water chlorination known to have higher oestrogenic activity than BPA, in dialysis water. Then, We have demonstrated that HDF leads to a higher risk of exposure to ED than HD, via the contamination of the liquid of substitution perfused in patient. These results will allow manufacturers to take into account the risk of contamination to these ED as well as physicians and pharmacists involved in patient care.Very few data are available regarding the clinical impact of such exposition on dialysed patient and no study has included the risk arising from ClxBPA. Therefore, we have performed exposure biomarkers using ultra-sensitive analytical methods to determine BPA and ClxBPA concentration in urine and plasma. These biomarkers will allow studying the impact of different dialysis techniques on patient exposure to these ED.

<p>Mikroplastika&nbsp; je&nbsp; sveprisutna&nbsp; u&nbsp; vodenom&nbsp; ekosistemu&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; često<br />ističe značaj ispitivanja njihovog uticaja na pona&scaron;anje drugih jedinjenja u vodi.<br />Pod pojmom mikroplastika podrazumevaju se plastične čestice manje od 5 mm.<br />Imajući u vidu potrebu za unapređenjem znanja o &scaron;tetnom uticaju mikroplastike<br />u životnoj sredini u ovom radu sproveden je set eksperimenata u kom je ispitivan<br />mehanizam&nbsp; interakcija&nbsp; koje&nbsp; se&nbsp; uspostavljaju&nbsp; prilikom&nbsp; adsorpcije&nbsp; hlorovanih<br />fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na mikroplastici&nbsp; u&nbsp; vodenom&nbsp; matriksu.&nbsp; Kako&nbsp; bi&nbsp; se&nbsp; &scaron;to&nbsp; detaljnije&nbsp; razumeo&nbsp; uticaj mikroplastike&nbsp; i&nbsp; osobina&nbsp; vodenog&nbsp; matriksa&nbsp; na&nbsp; pona&scaron;anje&nbsp; organskih&nbsp; polutanata, laboratorijska ispitivanja su sprovedena u sintetičkom i realnom vodenommatriksu.&nbsp; Takođe&nbsp; je&nbsp; sprovedena&nbsp; optimizacija&nbsp; izolovanja&nbsp; i&nbsp; karakterizacije mikroplastike iz kozmetičkih sredstava u cilju procene uticaja osobina primarne mikroplastike na uspostavljanje interakcija sa organskim polutantima. Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; istraživanja&nbsp; može&nbsp; se&nbsp; zaključiti&nbsp; da&nbsp; se optimalna metoda izolovanja mikroplastike iz kozmetičkih sredstava zasniva na dodatnom&nbsp; tretiranju&nbsp; osu&scaron;enog&nbsp; materijala&nbsp; 30%&nbsp; vodonik-peroksidom,&nbsp; nakon ekstrakcije&nbsp; sredstva&nbsp; u&nbsp; destilovanoj&nbsp; vodi,&nbsp; u&nbsp; cilju&nbsp; dobijanja&nbsp; čistijih&nbsp; uzoraka mikroplastike. Promena brzine me&scaron;anja ima znčajan uticaj na promenu stepena adsorpcije ispitivanih grupa organskih jedinjenja.&nbsp; Uticaj se ogleda u povećanju stepena adsorpcije sa porastom brzine me&scaron;anja, a maksimalni procenat adsorpcije postignut&nbsp; je&nbsp; pri&nbsp; brzini&nbsp; me&scaron;anja&nbsp; od&nbsp; 150&nbsp; o/min.&nbsp; Dodatno,&nbsp; disperzija&nbsp; pra&scaron;kastih materijala u vodi nema značajan uticaj na promenu stepena adsorpcije hlorovanih fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na mikroplastici.Ravnotežno&nbsp; stanje&nbsp; između&nbsp; koncentracije&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata<br />benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; u&nbsp; vodi&nbsp; i&nbsp; odabranih predstavnika&nbsp; mikroplastike&nbsp; (PEp,&nbsp; PE_PCPs_1,&nbsp; PE_PCPs_2,&nbsp; PEg,&nbsp; PET,&nbsp; PP&nbsp; i PLA) uspostavlja se nakon 24 i 48 h kontakta u zavisnosti od vrste jedinjenja. Na promenu&nbsp; adsorpcionog&nbsp; afiniteta&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata&nbsp; benzena&nbsp; i policikličnih aromatičnih ugljovodonika prema mikroplastici utiču kako fizičkohemijske&nbsp; osobine&nbsp; jedinjenja&nbsp; tako&nbsp; i&nbsp; karakteristike&nbsp; mikroplastike.&nbsp; Na&nbsp; osnovu kinetičkih&nbsp; eksperimenata, najveći adsorpcioni afinitet ka mikroplastici&nbsp; ispoljili su&nbsp; derivati&nbsp; benzena&nbsp; (qt=103-350&nbsp; &micro;g/g),&nbsp; dok&nbsp; je&nbsp; najmanji&nbsp; uočen&nbsp; kod&nbsp; hlorovanih fenola&nbsp; (qt=25-225&nbsp; &micro;g/g).&nbsp; Dobijeni&nbsp; rezultati&nbsp; adsorpcije&nbsp; derivata&nbsp; benzena&nbsp; na ispitivanim&nbsp; česticama&nbsp; mikroplastike&nbsp; takođe&nbsp; su&nbsp; ukazali&nbsp; na&nbsp; veći&nbsp; afinitet&nbsp; ovih jedinjenja&nbsp; ka&nbsp; mikroplastici,&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; jedinjenjima&nbsp; iz&nbsp; grupe&nbsp; policikličnih aromatičnih&nbsp; ugljovodonika&nbsp; i&nbsp; hlorovanih&nbsp; fenola&nbsp; sličnih&nbsp; logKow&nbsp; vrednosti. Dodatno,&nbsp; uticaj&nbsp; vodenog&nbsp; matriksa&nbsp; na&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na&nbsp; mikroplastici&nbsp; zavisi&nbsp; od same grupe jedinjenja kao i od vrste mikroplastike pri čemu je najmanje izražen u&nbsp; slučaju&nbsp; ispitivanih&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika,&nbsp; a&nbsp; najvi&scaron;e&nbsp; kod hlorovanih fenola.Visoke&nbsp; vrednosti&nbsp; koeficijenta&nbsp; determinacije&nbsp; kinetičkog&nbsp; modela&nbsp; pseudodrugog&nbsp; reda&nbsp; za&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih aromatičnih ugljovodonika na čestice mikroplastike ukazjuju da je hemisorpcija mogući&nbsp; mehanizam.&nbsp; Pored&nbsp; visokih&nbsp; vrednosti&nbsp; koeficijenata&nbsp; determinacije&nbsp; u slučaju svih odabranih organskih jedninjenja dobijena konstanta brzine drugog reda&nbsp; bila&nbsp; je&nbsp; manja&nbsp; od&nbsp; po četne&nbsp; brzine&nbsp; adsorpcije&nbsp; &scaron;to&nbsp; ukazuje&nbsp; na&nbsp; znatno&nbsp; brže odvijanje&nbsp; adsorpcije&nbsp; pri&nbsp; kraćim&nbsp; vremenima&nbsp; kontakta&nbsp; (12-24&nbsp; h)&nbsp; nakon&nbsp; čega&nbsp; je<br />dolazilo do usporavanja procesa adsorpcije.Mehanizam adsorpcije hlorovanih fenola, derivata benzena i policikličnih aromatičnih ugljovodonika&nbsp; ispitivan&nbsp; je primenom Freundlich-ovog, Langmuirovog,&nbsp; Redlich-Peterson-ovog&nbsp; i&nbsp; Dubinine-Radusckevich-evog&nbsp; adsorpcionog modela. Vrednosti Freundlich-ovog eksponenta za adsorpciju hlorovanih fenola, derivata benzena i&nbsp; policikličnih aromatičnih ugljovodonika bile su manje od 1,<br />&scaron;to ukazuje na to da je slobodna energije adsorpcije na mikroplastci opadala sa povećanjem&nbsp; inicijalne&nbsp; koncetracije&nbsp; ispitivanih&nbsp; polutanata.&nbsp; Vrednosti maksimalnog adsorpcionog kapaciteta dobijene za&nbsp; adsorpcione procese PAH&nbsp; na česticama mikroplastike bile su u opsegu od 29,7-2596,5 &micro;g/g. Visoke vrednosti maksimalnih adsorpcionih kapaciteta dobijene su takođe za adsorpciju derivata benzena na ispitivanim vrstama mikroplastike&nbsp; 39,3-2010,1 &micro;g/g. S druge strane, uočeno&nbsp; je&nbsp; različito&nbsp; adsorpciono&nbsp; pon&scaron;anje&nbsp; hlorovanih&nbsp; fenola&nbsp; u&nbsp; zavisnosti&nbsp; od vodenog metriksa u kom su eksperimenti sprovedeni pri čemu su&nbsp; qmax&nbsp; vrednosti iznosile 20,00-205,6 &micro;g/g. Značajan uticaj&nbsp; pH vrednosti vodenog matriksa&nbsp; utvrđen je&nbsp; za adsorpciju hlorovanih&nbsp; fenola&nbsp; na&nbsp; mikroplastici,&nbsp; dok&nbsp; u&nbsp; slučaju&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; PAH promena pH vrednosti vodenog matriksa nije pokazala značajan uticaj. Rezultati dobijeni&nbsp; za&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola&nbsp; na&nbsp; mikroplastici&nbsp; ukazuju&nbsp; na&nbsp; nižu tendenciju&nbsp; ka&nbsp; formiranju&nbsp; interakcija&nbsp; hlorovanih&nbsp; fenola&nbsp; sa&nbsp; česticama mikroplastike pri pH 4 i pH 10, pri čemu se stepen adsorpcije kretao u opsegu od 8-35% i 15-35%, respektivno, u odnosu na pH 7 (55-65%). Najniži&nbsp; adsorpcioni&nbsp; afinitet&nbsp; uočava&nbsp; se&nbsp; pri&nbsp; adsorpciji&nbsp; ispitivanih&nbsp; grupa jedinjenja na PLA. Može se pretpostaviti da će se organski polutanti,&nbsp;&nbsp; ukoliko ova vrsta mikroplastike dospe u vodene sisteme, slabo vezivati na ovaj materijal pri čemu će značajno manje uticati na njihov trasport kroz životnu sredinu, u odnosu<br />na druge ispitivane vrste mikroplastike. Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; istraživanja&nbsp; može&nbsp; se&nbsp; zaključiti&nbsp; da&nbsp; na adsorpciju ispitivanih grupa organskih jedinjenja i mikroplastike značajan uticaj imaju&nbsp; fizičko-hemijske&nbsp; osobine&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; kao&nbsp; &scaron;to&nbsp; su&nbsp; kiselinska konstanta, veličina molekula, hidrofobnost, stukturni raspored i dr. Pored toga, karakteristike vodenog matriksa, među kojima je najvažnija pH vrednost, imaju značajan&nbsp; uticaj&nbsp; na&nbsp; adsorpcioni&nbsp; afinitet&nbsp; jedinjenja&nbsp; ka&nbsp; mikroplastici.&nbsp; Dodatno,<br />struktura&nbsp; i&nbsp; poreklo&nbsp; polimera&nbsp; ima&nbsp; veliki&nbsp; uticaj&nbsp; na&nbsp; formiranje&nbsp; interakcija&nbsp; sa<br />ispitivanim grupama organskih polutanata. Dobijeni rezultati takođe ukazuju na<br />nemogućnost&nbsp; određivanje&nbsp; unifomnog&nbsp; mehanizma&nbsp; adsorpcije&nbsp; organskih<br />jedinjenja na česticama mikroplastike u vodi.</p> / <p>Microplastics&nbsp; are&nbsp; ubiquitous&nbsp; in&nbsp; aquatic&nbsp; ecosystems,&nbsp; so&nbsp; it&nbsp; is&nbsp; essential&nbsp; to study their&nbsp; impact on the behaviour of other compounds which are commonly present in water. The term microplastics refers to all plastic particles smaller than 5 mm. In order&nbsp; to address knowledge gaps relating to the potential harmful effects of microplastics in the environment, the experiments conducted during this thesis were designed to investigate the adsorption mechanism of chlorinated phenols, benzene derivatives, and polycyclic aromatic hydrocarbons on microplastics in water.&nbsp; To&nbsp; provide&nbsp; a&nbsp; more&nbsp; detailed&nbsp; understanding&nbsp; of&nbsp; the&nbsp; influence&nbsp; of&nbsp; different water&nbsp; matrices&nbsp; on&nbsp; adsorption&nbsp; properties&nbsp; of&nbsp; microplastics,&nbsp; experiments&nbsp; were conducted in both synthetic and real water matrices. In the course of this work, methods were optimised for the isolation and characterization of microplastifrom personal care products, in order to allow investigation&nbsp; of the influence of the&nbsp; properties&nbsp; of&nbsp; primary&nbsp; microplastics&nbsp; on&nbsp; their&nbsp; interactions&nbsp; with&nbsp; organic pollutants.Base on the obtained results, it can be concluded that the optimal method of isolating microplastics from personal care products is based&nbsp; on treating already dried&nbsp; material&nbsp; with&nbsp; 30%&nbsp; hydrogen&nbsp; peroxide,&nbsp; after&nbsp; extraction&nbsp; of&nbsp; the&nbsp; agent&nbsp; in distilled water, in order to obtain cleaner microplastic samples. The mixing rate was&nbsp; found&nbsp; to&nbsp; have&nbsp; a&nbsp; significant&nbsp; effect&nbsp; on&nbsp; the&nbsp; degree&nbsp; of&nbsp; adsorption&nbsp; of&nbsp; the investigated&nbsp; organic&nbsp; compounds.&nbsp; Increasing&nbsp; the&nbsp; mixing&nbsp; speed&nbsp; led&nbsp; to&nbsp; a&nbsp; higher<br />degree&nbsp; of&nbsp; adsorption,&nbsp; with&nbsp; the&nbsp; maximum&nbsp; adsorption&nbsp; percentage&nbsp; reached&nbsp; at&nbsp; a<br />mixing speed of 150 rpm. In addition, the dispersion of powdered materials in the&nbsp; water&nbsp; had&nbsp; no&nbsp; significant&nbsp; effect&nbsp; on the&nbsp; degree&nbsp; of&nbsp; adsorption&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on microplastics.<br />The&nbsp; adsorption&nbsp; equilibrium&nbsp; between&nbsp; the&nbsp; concentration&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene derivatives and polycyclic aromatic hydrocarbons in water and selected types of microplastics (PEp, PE_PCPs_1, PE_PCPs_2, PEg, PET, PP, and&nbsp; PLA) was established after 24 and 48 h of contact time, depending on the selected&nbsp; group&nbsp; of&nbsp; organic&nbsp; pollutants.&nbsp; The&nbsp; adsorption&nbsp; affinity&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; towards microplastics&nbsp; was&nbsp; influenced&nbsp; by&nbsp; both&nbsp; the&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; the compounds&nbsp; and&nbsp; the&nbsp; characteristics&nbsp; of&nbsp; the&nbsp; microplastics.&nbsp; Based&nbsp; on&nbsp; the&nbsp; kinetic experiments,&nbsp; the&nbsp; highest&nbsp; adsorption&nbsp; affinity&nbsp; for&nbsp; microplastics&nbsp; was&nbsp; shown&nbsp; by benzene derivatives (qt=103-350 &micro;g/g), while the lowest was&nbsp; observed during the adsorption of chlorinated phenols (qt=25-225 &micro;g/g). Benzene derivatives showed higher&nbsp; adsorption&nbsp; affinities&nbsp; for&nbsp; the&nbsp; selected&nbsp; microplastic&nbsp; particles&nbsp; than&nbsp; the polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; and&nbsp; &nbsp; chlorinated&nbsp; phenols&nbsp; which&nbsp; had&nbsp; similar logKow&nbsp; values. The influence of the water matrix on adsorption of chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on microplastics&nbsp; depended&nbsp; on&nbsp; the&nbsp; specific&nbsp; functional&nbsp; groups&nbsp; of&nbsp; the&nbsp; investigated compounds as well as on the type of microplastics. Water matrix had little impact on&nbsp; the&nbsp; adsorption&nbsp; of&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on&nbsp; microplastics&nbsp; but greatly impacted the adsorption of chlorinated phenols. Fitting the pseudo-second order kinetic&nbsp; model to the&nbsp; adsorption data of chlorinated phenols, benzene derivatives, and polycyclic aromatic hydrocarbons on microplastic particles resulted in high correlation coefficients, indicating that chemisorption&nbsp; is&nbsp; the&nbsp; likely&nbsp; adsorption&nbsp; mechanism.&nbsp; In&nbsp; addition&nbsp; to&nbsp; the&nbsp; high correlation coefficients obtained for all the organic pollutants investigated, the pseudo-second order rate constants obtained were lower than the initiaadsorption rate, indicating significantly faster adsorption at shorter contact times (12-24 h), with adsorption slowing down as equilibrium was reached.The adsorption mechanism of chlorinated phenols, benzene derivatives,<br />and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; was&nbsp; investigated&nbsp; using Freundlich,Langmuir,&nbsp; Redlich-Peterson,&nbsp; Dubinine-Radusckevich,&nbsp; and&nbsp; Temkin&nbsp; adsorption models.&nbsp; The&nbsp; Freundlich&nbsp; exponent&nbsp; values&nbsp; for&nbsp; the&nbsp; adsorption&nbsp; of&nbsp; chlorinated phenols, benzene&nbsp; derivatives, and polycyclic&nbsp; aromatic&nbsp; hydrocarbons were&nbsp; less than 1 which indicates that the free energy of adsorption of these compounds on microplastics&nbsp; decreases&nbsp; as&nbsp; the&nbsp; initial&nbsp; concentration&nbsp; increases.&nbsp; The&nbsp; maximum adsorption capacities of PAHs on microplastic particles were in the range of 29.7-2596.5&nbsp; &micro;g/g.&nbsp; High&nbsp; maximum&nbsp; adsorption&nbsp; capacities&nbsp; were&nbsp; also obtained&nbsp; for the adsorption&nbsp; of&nbsp; benzene&nbsp; derivatives&nbsp; on&nbsp; the&nbsp; tested&nbsp; types&nbsp; of&nbsp; microplastics:&nbsp; 39.3-2010.1&nbsp; &micro;g/g.&nbsp; The&nbsp; chlorinated&nbsp; phenols&nbsp; behaved&nbsp; differently,&nbsp; and&nbsp; were&nbsp; more effected by the water matrix, with qmax values in&nbsp; the range 20.00-205.6 &micro;g/g. The pH of the water matrix was found to have a significant effect on the adsorption&nbsp; of&nbsp; chlorinated&nbsp; phenols&nbsp; on&nbsp; microplastics,&nbsp; whereas&nbsp; in&nbsp; the&nbsp; case&nbsp; of benzene&nbsp; derivatives&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons,&nbsp; the&nbsp; degree&nbsp; of<br />adsorption&nbsp; was&nbsp; largely&nbsp; independent&nbsp; of&nbsp; the&nbsp; water&nbsp; pH.&nbsp; For&nbsp; the&nbsp; adsorption&nbsp; of chlorinated&nbsp; phenols&nbsp; on&nbsp; microplastics,&nbsp; neutral&nbsp; pH&nbsp; conditions&nbsp; resulted&nbsp; in&nbsp; the greatest degrees of adsorption (55-65% at pH 7), while adsorption was inhibited under acidic (8-35% at pH 4) and basic (15-35% at pH 10) conditions. The microplastic type with the lowest observed adsorption affinities was PLA. It can be thus be assumed that in the event that this type of microplastic enters water systems, organic pollutants will only adsorb weakly to this material, such&nbsp; that&nbsp; it&nbsp; will&nbsp; have&nbsp; significantly&nbsp; less&nbsp; impact&nbsp; on&nbsp; the&nbsp; transport&nbsp; of&nbsp; the se compounds through the environment, than the other tested&nbsp; types of microplastics. The results obtained in this research demonstrate that the adsorption of the selected&nbsp; groups&nbsp; of&nbsp; organic&nbsp; pollutants&nbsp; on&nbsp; the&nbsp; microplastics&nbsp; investigated&nbsp; is significantly&nbsp; controlled&nbsp; by&nbsp; the&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; the&nbsp; tested compounds, such as the dissociation constant, molecule&nbsp; size, hydrophobicity,<br />structural properties, etc. In addition, the characteristics of the water matrix play an important role in controlling adsorption of organic pollutants on microplastic, especially the water pH. In addition, the structure and aging of the polymers had a major influence&nbsp; on their interactions with the selected organic pollutants. The obtained&nbsp; results&nbsp; also&nbsp; demonstrate&nbsp; the&nbsp; difficulty&nbsp; in&nbsp; determining&nbsp; a&nbsp; uniform mechanism&nbsp; of&nbsp; adsorption&nbsp; between&nbsp; the&nbsp; various&nbsp; organic&nbsp; compounds&nbsp; and microplastic particles in water.</p>

This study evaluated the effects of chlorinated effluent discharged from the City of Denton, Texas' wastewater treatment plant on Pecan Creek's fish and macroinvertebrate assemblages, and their recovery upon dechlorination. A baseline of ecological conditions was established while chlorine was present in the effluent (June 1993- October 1993), and was evaluated again after dechlorination with sulfur dioxide (October 1993-August 1994). In situ Asiatic clam and fathead minnow ambient toxicity tests, and fish and macroinvertebrate collections were used to establish this baseline for comparison to post-dechlorination results.

Hur kan livscykelanalyser bistå riskvärderingen vid val av åtgärdsmetod? I det här examensarbetet undersöktes hur resultaten från livscykelanalyser kan användas i beslutstödsverktyget SAMLA för förorenade områden för att bistå val av åtgärdsmetod vid Finspångs centraltvätt. Examensarbetet har genomförts i samarbete med Structor Miljö Öst AB. Livscykelanalyser har utförts för två olika typer av åtgärdsmetoder in situ, stimulerad anaerob reduktiv deklorering samt elektrisk konduktiv uppvärmning. Tidigare studier har visat att olika livscykelanalysmetoder ger olika resultat. Även den här studien bekräftar det. Därför bör inte resultat från olika metoder jämföras. Livscykelanalyser kompletterar SAMLA för förorenade områden väl. De procentuella förhållandena beräknades mellan åtgärdsmetodernas miljö- och klimatpåverkan. I värderingssteget i SAMLA bedöms åtgärdsalternativens påverkan i jämförelse med nollalternativet. En bedömning gjordes av respektive åtgärdsalternativ och korrigering av förhållandet mellan metoderna utfördes genom att samma procentuella förhållande som beräknats fram för miljöbelastningen respektive klimatpåverkan beräknades för värderingspoängen. Med stöd av livscykelanalyser samt riskvärdering bör efterbehandlingsmetoden stimulerad anaerob reduktiv deklorering väljas för Finspångs centraltvätt. / How can life cycle analyzes assist the risk assessment when choosing a remediation method? In this thesis, it was investigated how the results from life cycle analyzes can be used in the decision support tool SAMLA for contaminated sites to assist in the choice of remediation method at Finspång's Centraltvätt. The thesis has been carried out in collaboration with Structor Miljö Öst AB. Life cycle analyzes have been performed for two different types of in situ remediation methods, Enhanced Reductive Dechlorination and Electrical Conductive Heating. Previous studies have shown that different life cycle analysis methods lead to different results. This study also confirms this. Therefore, results from different methods should not be compared. Life cycle analyzes complement SAMLA for contaminated sites. The percentage ratios were calculated between the remediation methods' environmental and climate impact. In the valuation step in SAMLA, the impact of the remediation alternatives is assessed in comparison with the no action alternative. An assessment was made of the respectively remediation alternatives and a correction of the relationship between the methods was performed by calculating the same percentage ratio that was calculated for the valuation points of the environmental and climate impact. With the support of the life cycle analysis and the risk assessment the remediation method Enhanced Reductive Dechlorination should be chosen for Finspång's Centraltvätt.

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Cotutelle Québec-France. J'ai effectué une cotutelle de thèse entre l'Université de Montréal (Québec) et l'Université de Poitiers (France). / Les dérivés chlorés du Bisphénol A (ClxBPA) sont des polluants émergents qui possèdent des effets perturbateurs endocriniens. Lors du traitement de l’eau potable par chloration, le Bisphénol A (BPA) présent dans l’environnement peut réagir avec les molécules de chlore pour former des dérivés chlorés (ClBPA, Cl2BPA, Cl3BPA et Cl4BPA) ou ClxBPA. Ils sont présents dans divers milieux aquatiques tels que eaux usées et l’eau potable. Ces polluants émergents ont également été retrouvés chez l’humain, dans l’urine, le colostrum et le tissu placentaire. Dans une étude transversale, la présence de concentrations urinaires élevées de ClxBPA chez l’humain a été positivement associée au diabète de type 2. Les ClxBPA ont aussi été associés à l’obésité et à l’infarctus du myocarde. Dans la littérature, il n’existait que très peu de données sur la toxicocinétique des ClxBPA chez l’animal ou chez l’humain. Cette recherche doctorale vise à évaluer le risque lié à ces polluants émergents en déterminant les constantes métaboliques des ClxBPA, puis en élaborant une méthode analytique des métabolites du 3,3’-Cl2BPA par HPLC-MS/MS pour finalement valider un modèle pharmacocinétique à base physiologique (PBPK) chez l’animal. Dans un premier temps, les constantes métaboliques (Km, Vmax et la clairance intrinsèque) ont été déterminées à l’aide d’expérience in vitro avec des hépatocytes de rats et d’humain. Les essais ont révélé que les constantes métaboliques des ClxBPA peuvent varier considérablement en fonction des substances et des espèces. Ces expériences in vitro ont montré que la chloration avait un impact sur la clairance intrinsèque hépatique des ClxBPA chez les rats et les humains. Deuxièmement, nous avons développé une méthode analytique pour les métabolites du 3,3’-Cl2BPA par HPLC-MS/MS dans le plasma à l’Université de Poitiers. Nous avons pu valider cette méthode avec des échantillons de rats et d’humain. Les résultats ont montré que chez le rat Sprague-Dawley après administration i.v., le 3,3’-Cl2BPA-glucuronide est largement présent par rapport au 3,3’-Cl2BPA-sulfate. Pour l'humain, seul le 3,3’-Cl2BPA-G-d12 a été quantifié. Finalement, nous avons utilisé des méthodes in vitro (dialyse à l’équilibre) et in silico pour les paramètres physico-chimiques de chaque ClxBPA. Enfin, nous avons construit des modèles PBPK afin de simuler la pharmacocinétique i.v. chez le rat Sprague-Dawley pour chaque dérivé chloré. Deux modèles PBPK ont été développés : un avec le ClBPA, le Cl2BPA et le Cl3BPA versus le Cl4BPA avec un modèle à diffusion limitée. Il a été validé par une expérience in vivo sur 80 rats Sprague-Dawley. Le modèle calibré a prédit les concentrations mesurées des ClxBPA dans le plasma, le cerveau et les muscles après l’administration de 4 et 40 mg/kg pour ClBPA et Cl2BPA; 0,4 et 4 mg/kg pour Cl3BPA et Cl4BPA. Ce projet doctoral a contribué à 1) déterminer les constantes métaboliques (Km, Vmax, Clairance intrinsèque) des ClxBPA, 2) de développer et valider une méthode analytique par HPLC-MS/MS des métabolites du Cl2BPA dans le plasma animal et humain et 3) de valider deux modèles PBPK chez le rat afin de connaitre la distribution plasmatique et tissulaire des ClxBPA. / Chlorinated derivatives of Bisphenol A (ClxBPA) are emerging pollutants with endocrine disrupting effects. During the treatment of drinking water by chlorination, Bisphenol A (BPA) present in the environment can react with chlorine molecules to form chlorinated derivatives (ClBPA, Cl2BPA, Cl3BPA and Cl4BPA) or ClxBPA. They are present in various aquatic environments such as wastewater and drinking water. These emerging pollutants have also been found in humans, in urine, colostrum and placental tissue. In a cross-sectional study, high urinary ClxBPA levels in humans were positively associated with type 2 diabetes. ClxBPA has also been associated with obesity and myocardial infarction. In the literature, there was very limited data on the toxicokinetics of ClxBPA in animals or in humans. This doctoral research aims to assess the risk related to these emerging pollutants by determining the metabolic constants of ClxBPA and then developing an analytical method for 3,3'-Cl2BPA metabolites by HPLC-MS/MS to validate a physiologically based pharmacokinetic (PBPK) model in animals. First, metabolic constants (Km, Vmax, and intrinsic clearance) were determined using in vitro experiments with rat and human hepatocytes. The tests revealed that the metabolic constants of ClxBPA can vary considerably between substances and species. These in vitro experiments showed that chlorination impacted the intrinsic hepatic clearance of ClxBPA in rats and humans. Second, we developed an analytical method for 3,3'-Cl2BPA metabolites by HPLC-MS/MS in plasma at the University of Poitiers. We were able to validate this method with rat and human samples. The results demonstrated that in Sprague-Dawley rats after an i.v. administration, 3,3'-Cl2BPA-glucuronide is largely present compared to 3,3'-Cl2BPA-sulfate. For humans, only 3,3'-Cl2BPA-G-d12 was quantified. Finally, we used in vitro (equilibrium dialysis) and in silico methods for the physicochemical parameters of each ClxBPA. Finally, we constructed PBPK models to simulate the i.v. pharmacokinetics in Sprague-Dawley rats for each chlorinated derivative. Two PBPK models were developed: one with ClBPA, Cl2BPA and Cl3BPA versus Cl4BPA with a diffusion- limited model. It was validated by an in vivo experiment on 80 Sprague-Dawley rats. The calibrated model predicted measured ClxBPA concentrations in plasma, brain, and muscle after administration of 4 and 40 mg/kg for ClBPA and Cl2BPA: 0.4 and 4 mg/kg for Cl3BPA and Cl4BPA. This doctoral project contributed to 1) determine the metabolic constants (Km, Vmax, Intrinsic Clearance) of ClxBPA, 2) develop and validate an analytical method by HPLC-MS/MS of Cl2BPA metabolites in animal and human plasma and 3) validate two PBPK models in rats to understand the plasma and tissue distribution of ClxBPA.

L'objectif de cette thèse est de développer un procédé plasma qui puisse se substituer au procédé de dépôt électrolytique de laiton, actuellement appliqué sur les fils d'acier utilisés comme matériaux de renforcement dans un pneu, pour les faire adhérer au caoutchouc. La stratégie employée consiste à déposer une couche mince organochlorée en continu sur un fil d'acier zingué, qui traverse une décharge à barrière diélectrique tubulaire, fonctionnant à la pression atmosphérique, dans une configuration fil-cylindre. Dans un premier temps, les travaux se concentrent sur la caractérisation de la décharge et de la couche mince déposée à la fois en mode statique (substrat immobile dans le réacteur) et dynamique (substrat en défilement). Des relations sont établies entre les paramètres plasma (puissance dissipée dans la décharge, fréquence de la source haute tension, flux de précurseur), les propriétés de la décharge et les caractéristiques du revêtement plasma. Des études morphologique, cinétique et chimique de la couche mince sont réalisées. Dans un second temps, la préparation de la surface du substrat et le dépôt plasma sont optimisés pour permettre d'obtenir les meilleurs niveaux d'adhésion entre l'acier zingué et le caoutchouc. À l'issue de ce travail d'optimisation, des analyses sont réalisées pour identifier la nature de la nouvelle interphase d'adhésion. Cette étude se conclut alors par une discussion sur l'origine possible des liens qui s'opèrent dans ce nouveau système / The primary objective of this thesis project is to develop a plasma process able to replace the electrolytic brass plating process, which is currently performed on steel wires used as reinforcing materials in tires to make them bond with rubber. The chosen strategy consists in depositing organo-chlorinated thin films in a continuous way on zinc-plated steel wires going across a tubular atmospheric pressure dielectric barrier discharge in a wire-cylinder configuration. In a first time, works focus on characterization of both the discharge and the plasma layer, deposited in the static (substrate stationary in the reactor) and dynamic (moving substrate) modes. Relationships are established between the plasma parameters (power dissipated in the discharge, high voltage source frequency, precursor flow rate), the discharge properties and the thin film characteristics. Morphological, kinetic and chemical studies of the plasma layer are carried out. In a second time, the substrate surface preparation and the coating are optimized to enhance the adhesion between zinc-plated steel wires and rubber. Analyses are performed to identify the new adhesion interface nature. At the end of this study, hypotheses concerning the adhesion origin in this system are formulated