Sr-90 and Cs-137 are two key fission products that are important in a number of radioactive waste or contamination clean-up scenarios. This thesis investigates the sorptiondesorption behaviour of these two radionuclides with a number of sorbents relevant to one of the legacy waste storage ponds on the Sellafield site. Sorption-desorption studies were undertaken on brucite (Mg(OH)2), UO2 and UO3 powders to represent components of the fine particulate sludge that has accumulated on the bottom of the pond, resulting from corrosion of the Magnox fuel elements. Brucite was found not to have a significant interaction with Sr-90 or Cs-137. However, organic molecules in the form of humic acid and Pseudanabaena catenata cyanobacterial growth supernatant were both found to enhance sorption interactions of Sr-90 with brucite. The effect of humic acid was pH dependent and appeared to control both sorption and desorption behaviour at pH 11.5. Uranium oxides had the most significant effect on controlling Sr-90 and Cs-137 sorption-desorption behaviour. In this work X-Ray Absorption Spectroscopy (XAS) showed that 90Sr sorbed strongly to both uranium oxides as a bidentate inner-sphere complex. Humic acid did not appear to alter the interaction of Sr-90 with UO2. For Cs-137 there was a significant, reversible interaction with both oxides, although the interaction was far stronger with UO3. Successful detection of stable Sr and Cs isotopes on uranium oxides was achieved with Laser Induced Breakdown Spectroscopy (LIBS).

Increasing concern about the pollution of environment by inorganic and organic chemicals arising from naturally occurring ecological events and industrial processes has created a need for the search of new techniques in the removal of these contaminants. One of the natural material that can be used in such processes is clay. Clay minerals have large surface areas and high cation exchange capacities which enables them to be modified by cationic surfactants. The material prepared, often called as &amp / #8216 / organoclay&amp / #8217 / , can be used to remove hydrophobic organic and anionic contaminants from polluted water. Among the anionic contaminants, oxyanions such as nitrate, chromate are detrimental to human life and environment even at &micro / g/L- mg/L levels. Application of organoclays for their removal from polluted water appears as one of the practical and rather cheap solution. In this study, a local clay from Ankara-Kalecik (Han&ccedil / ili Bentonite) was modified by hexadecyltrimethylammonium bromide (HDTMA-Br) to a level of twice of its cation exchange capacity. This process alters the negatively charged surface of the clay into a positively charged one, providing sites for the removal of anionic contaminants. In this study, the degree of HDTMA+ uptake by the clay within a period of eight hours is found to be 97% of the initial amount added. In desorption studies it was revealed that only about 1% of the sorbed HTDMA+ was leached in a seven days of water-organoclay interaction revealing a rather stable organoclay structure in aqeous media. Sorption experiments with nitrate, borate, and chromate solutions were performed in order to determine the anion sorption capacity of the organoclays prepared. It turns out that while untreated clay has insignificant capacity, the modified clay can remove considerable amount of nitrate and chromate ions from aqeous solutions. While the nitrate sorption was increased about eleven fold, change in chromate sorption was reached to a level of twenty fold compared to that of the untreated clay. Sorption data for nitrate and chromate are both well described by the Langmuir isotherms. No significant change was observed in case of borate-organoclay interaction. Desorption of nitrate and chromate ions from organoclay surface were also investigated. Sorption of these oxyanions were found to be almost irreversible in aqeous media. The results imply that a properly prepared organoclay can be used for the removal of oxyanions, such as nitrate and chromate from polluted water systems.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2007. / Härtill 4 uppsatser.

<p>U okviru ovog istraživanja ispitani su: 1. Optimalni uslovi&nbsp; za<br />eksperimente biodegradacije policikličnih aromatičnih ugljovodonika sa istim i<br />različitim brojem prstenova; 2. Uticaj struture&nbsp; i matriksa na biodegradaciju<br />policikličnih aromatičnih ugljovodonika sa istim brojem prstenova; 3.<br />Fitotoksičnost biljaka&nbsp; (testovi klijavosti i usvajanje policikličnih aromatičnih<br />ugljovodonika); 4. Procena&nbsp; potencijalne&nbsp; biodostupne frakcije primenom<br />različitih hemijskih sorbenata (HPCD, &beta;CD&nbsp; i&nbsp; MCD, XAD4 i TenaxTA)&nbsp; i 5.<br />Korelacija dobijenih rezultata&nbsp; testovima biodegradacije, testovima klijavosti,<br />testovima fitotoksičnosti i rezultata dobijenih iz eksperimenta procene<br />biodostupnosti hemijskim testovima.&nbsp; Rezultati su pokazali da se&nbsp; optimalni<br />uslovi za biodegradaciju&nbsp; postižu dodatkom mineralnih medijuma, inokuluma i<br />surfaktanata.&nbsp; Posmatrajući uticaj sadržaja gline i organske materije i strukture<br />molekula,&nbsp; najveći stepen biorazgradnje ima fluoranten, &scaron;to je u skladu sa<br />njegovim fizičko-hemijskim osobinama, dok se sadržaj pirena i krizena nije<br />mogao jasno korelirati sa sadržajem organske materije i gline.&nbsp; &Scaron;to se tiče<br />testova fitotoksičnosti,&nbsp; sva semena su proklijala, &scaron;to govori u prilog tome&nbsp; da<br />me&scaron;avina ovih kontaminanata&nbsp; pri ispitivanim koncentracijama&nbsp; nije inhibirala<br />klijanje biljaka.&nbsp; Testovi usvojivosti ispitivanih PAH-ova su pokazali da je<br />najmanji procenat usvojivosti semenom dobijen za benzo(a)piren, &scaron;to se može<br />objasniti njegovom kompleksnijom strukturom. Hemijskim testovima za<br />procenu biodostupnosti je sa druge strane pokazano da se desorpcija u prisustvu<br />MCD, XAD4 smole i Tenaxa može koristiti kao jednostavna metoda za procenu<br />potencijalne biodostupne&nbsp; frakcije organskih jedinjenja u sistemima sediment&nbsp; -voda.</p> / <p>The aim of this study was to investigate: 1. The optimal conditions for&nbsp;the biodegradation of polycyclic aromatic hydrocarbons with the same and&nbsp;different numbers of rings; 2. The impact of structure and matrix&nbsp;biodegradation of polycyclic aromatic hydrocarbons with the same number of&nbsp;rings; 3. Phytotoxicity (germination tests and polycyclic aromatic hydrocarbon&nbsp;uptake); 4. The means for assessing the bioavailable fractions using various&nbsp;chemical sorbents (HPCD, &beta;CD, MCD, XAD4 and &nbsp;TenaxTA) and 5. The&nbsp;correlation between the results of the biodegradation tests, germination tests,&nbsp;phytotoxicity tests and the results obtained from the experiments in the&nbsp;assessment of bioavailability and chemical tests. The results showed that the&nbsp;optimal conditions for biodegradation are achieved by the addition of mineral&nbsp;media, inoculum and surfactants. When considering the effect of the contents of&nbsp;clay and organic matter and the structure of the molecules, the highest degree of&nbsp;biodegradation was observed with fluoranthene,&nbsp; which is in line with its&nbsp;physico-chemical properties. The concentrations of pyrene and chrysene were&nbsp;not clearly correlated with the organic matter and clay contents. During thephytotoxicity tests, all seeds sprouted, which speaks in favor of a mixture of&nbsp;these contaminants not inhibiting the germination of the plants. Tests for the&nbsp;uptake of the investigated PAHs showed that the lowest percentage seed uptake&nbsp;was for benzo(a)pyrene, which is explained by its more complex structure.&nbsp;Chemical tests for evaluating bioavailability have shown that desorption in the&nbsp;presence of MCD, XAD4 and Tenax resins can be used as a simple method for&nbsp;the evaluation of a potential bioavailable fraction of organic compounds in&nbsp;water-sediment systems.</p>

Master of Science / Department of Civil Engineering / Alok Bhandari / In the upper Midwest, subsurface tile drainage water is a major contributor of nitrate (NO[subscript]3–N) coming from fertilizers and animal manure. Movement of NO[subscript]3-N through tile drainage into streams is a major concern as it can cause eutrophication and hypoxia conditions, as in the Gulf of Mexico. Denitrifying bioreactors is one of the pollution control strategies to treat contaminated tile drainage water. These bioreactors require four conditions which are: 1) organic carbon source, 2) anaerobic conditions, 3) denitrifying bacteria and 4) influent NO[subscript]3-N. This research focuses on investigating fate of veterinary antibiotics in woodchips commonly used in in-situ reactors. Tylosin (TYL) and sulfamethazine (SMZ) are two veterinary antibiotics which are most commonly used in the United States and can be found in tile water after manure is land applied. Partition coefficients of TYL and SMZ on wood were determined by sorption experiments using fresh woodchips and woodchips from an in situ reactor. It was concluded that the woodchips were an effective means to sorb the veterinary antibiotics leached into the tile water after application of animal manure. Linear partition coefficients were calculated and phase distribution relationships were established for both the chemicals. The fresh woodchips gave inconclusive data but predictions could be made by the information determined in the experiments using woodchips from a ten year old woodchip bioreactor. Desorption was also studied and the likelihood of desorption was predicted using the Apparent Hysteresis Index. Overall, it was found that the old woodchips allowed for quick sorption of both antibiotics. It was also found that SMZ had reversible sorption on old woodchips. Thus, it was concluded that the woodchip bioreactor would not be effective for removal of veterinary antibiotics from tile drainage. More research is required for the fate of TYL and to confirm the conclusion.

<p>Prirodna organska materija zemlji&scaron;ta/sedimenata predstavlja glavnu oblast<br />za sorpciju hidrofobnih organskih jedinjenja, a njene osobine utiču na stepen<br />retencije i konsekventnu (bio)dostupnost organskih jedinjenja. Da bi se procenio<br />ekotoksikolo&scaron;ki rizik zagađenih zemlji&scaron;ta/sedimenata po okolinu, dizajnirala<br />odgovarajuća strategija remedijacije ili predvidela sudbina i transport organskih<br />polutanata u zagađenim zonama, neophodno je razumevanje mehanizma sorpcije i<br />desorpcije na nivou mehanizma uspostavljenih veza. U radu je izvr&scaron;eno ispitivanje<br />sorpcije i desorpcije odabranih hidrofobnih organskih polutanata, pentahlorbenzena<br />i lindana, na sekvencijalno ekstrahovanim huminskim kiselinama i huminima iz<br />jednog uzorka sedimenta u cilju pronalaženja veze između strukturnih<br />karakteristika izolovanih huminskih kiselina i humina i sorpcionih i desorpcionih<br />parametara. Afinitet za sorpciju, nelinearnost izotermi i prividna sorpciono-desorpciona histereza korelirani su&nbsp; sa osobinama sorbenata dobijenim iz<br />elementarne i FTIR spektroskopske analize. Predloženo je da je mehanizam<br />sorpcije na huminskim kiselinama rezultat odigravanja raspodele i specifične<br />adsorpcije, pri čemu se pri nižim koncentracijama pentahlorbenzena i lindana prvo<br />popune sorpciona mesta u kondenzovanoj aromatičnoj oblasti, a tek potom pri<br />vi&scaron;im koncentracijama sorpciona mesta u amorfnim alifatičnim oblastima.<br />Sveukupno vi&scaron;i koeficijenti nelinearnosti dobijeni za sorpciju pentahlorbenzena na huminskim kiselinama u odnosu na nelinearnost sorpcionih izotermi lindana, ukazuju na to da u ukupnoj sorpciji pentahlorbenzena veći značaj ima mehanizam raspodele i sme&scaron;tanje molekula pentahlorbenzena u hidrofobne &scaron;upljine huminskih kiselina, u odnosu na specifičnu adsorpciju. Ovi zaključci su potvrđeni rezultatima spektroskopskih istraživanja interakcija&nbsp; odabranih organskih jedinjenja i N-metilformamida. Predloženi mehanizam sorpcije ne može objasniti sorpciju pentahlorbenzena i lindana na uzorcima humina, većje pretpostavljeno da nelinearna sorpcija za uzorke humina može biti rezultat ostvarivanja povr&scaron;inskih interakcija, a visoki afinitet za sorpciju rezultat je raspodele organskih jedinjenja u amorfnim alifatičnim oblastima koje pružaju odlično okruženje za sorpciju.</p><p>U cilju daljeg proučavanja mehanizma sorpcije, izvr&scaron;eno je ispitivanje kinetike<br />desorpcije tri odabrana hidrofobna organskajedinjenja, pentahlorbenzena, lindana i<br />pentahloranilina, posredstvom&nbsp; čvrstog adsorbenta, XAD-4 makroporozne<br />jonoizmenjivačke smole. Na osnovu rezultata dobijenih za uzorak sedimenta i<br />frakciju &lt; 125 &micro;m za dva ravnotežna vremena (15 i 90 dana) i za sva odabrana<br />organska jedinjenja može se zaključiti da se za procenu potencijalne (bio)dostupne<br />frakcije organskih jedinjenja može koristiti jednostavna desorpcija u prisustvu<br />XAD-4 makroporozne jonoizmenjivačke smole i to na dva načina: (1) ekstrakcijom<br />sedimenta tokom 24 časa, kada frakcija koja se desorbuje odgovara frakciji<br />jedinjenja koja se nalazi u brzo-desorbujućem domenu organske materije, ili (2)<br />ekstrakcijom tokom 6 časova, kada frakcija koja se desorbuje odgovara polovini<br />one frakcije jedinjenja koja se nalazi u brzo-desorbujućem domenu organske<br />materije.</p> / <p>Natural organic matter of soil/sediment make the main region for&nbsp;sorption of hydrophobic organic compounds, ant its properties influence the degree&nbsp;of retention and, consequently, (bio)availability of organic compounds. In order to&nbsp;assess the ecotoxicological risks of contaminated soils/sediments to the&nbsp;environment and design the appropriate remediation strategy or predict the fate and&nbsp;transport of organic pollutants in contaminated zones, it is necessary to understand&nbsp;the mechanisms of sorption/desorption at the level of the mechanism of established&nbsp;bonds. Study of the sorption and desorption of selected hydrophobic organic&nbsp;pollutants, pentachlorobenzene and lindane, on sequentially extracted humic acids&nbsp;and humins from a single sediment sample with the aim of finding the relationship&nbsp;between the structural characteristics of the isolated humic acids and humin and&nbsp;sorption and desorption parameters. Sorption affinity, nonlinearity of isotherms,&nbsp;and apparent sorption-desorption hysteresis were correlated to the sorbent&nbsp;characteristics obtained from elemental analysis and FTIR spectroscopic data. The&nbsp;proposed sorption mechanism on humic acids assumes that at low concentrations&nbsp;of pentachlorobenzene and lindane the sorption sites in the condensed aromatic&nbsp;region are occupied first, and then, at their higher concentrations, the sorption sites&nbsp;in the amorphous and aliphatic regions. Generally higher nonlinearity coefficient obtained for the sorption of pentachlorobenzene on &nbsp;umic acids compared with the nonlinearity of sorption isotherms for lindane, indicate that in the overall sorption of pentachlorobenzene of higher significance is the &nbsp;echanism of distribution and insertion of pentachlorobenzene molecule into hydrophobic dips of humic acids, compared to specific adsorption. These conclusions were confirmed with the results of spectroscopic investigation of &nbsp;intermolecular interaction of chosen organic compounds and N-methylformamide.Since suggested sorption mechanism could not explain sorption of &nbsp;pentachlorobenzene and lindane onto humin samples, it is supposed that the nonlinearity can be a result of surface interactions, while the high sorption affinity is result of distribution of organic compounds in the amorphous aliphatic regions that offer an excellent environment for sorption.</p><p>With the aim of further insight into the sorption mechanism, investigation of&nbsp;desorption kinetics of three chosen hydrophobic organic compounds,&nbsp;pentachlorobenzene, lindane and pentachloroaniline, in the presence of &nbsp;soild&nbsp;adsorbent XAD-4 macroporous ion-exchange resin was performed. On the basis of&nbsp;the results obtained for sediment sample and fraction &lt; 125 &micro;m at two equilibrium&nbsp;times (15 and 90 days) and for all selected organic compounds, it can be concluded&nbsp;that the assessment of the potential (bio)avialable fraction of organic compounds&nbsp;may be obtained by using simple method of desorption in the presence of XAD-4&nbsp;macroporous ion-exchange resin, performed in two ways: (1) by sediment&nbsp;<br />extraction during 24 hours, when the desorbing fraction corresponds to the fraction&nbsp;of &nbsp;he compound that is found in the fast-desorbing domain of organic matter, or&nbsp;(2) by 6-hour extraction, when the desorbing fraction corresponds to one half of the&nbsp;fraction appearing in the fast-desorbing domain of the organic matter.</p>

Cette thèse porte sur le comportement d’un composé prioritaire au titre de la Directive Cadre sur l’Eau au niveau européen : le tributylétain (TBT) et ses métabolites (dibutylétain (DBT) et monobutylétain (MBT)). On s’intéresse plus particulièrement aux eaux usées domestiques lors de leur transit dans deux stations d’épuration par lagunage naturel (STEP), traitement adapté aux effluents provenant des zones faiblement urbanisées. Ce travail de thèse vient combler le manque de résultats scientifiques sur (1) le niveau des concentrations en butylétains dans les effluents domestiques des zones peu urbanisées en entrée des stations par lagunage et en sortie après traitement ; (2) l’efficacité du traitement par lagunage à éliminer les butylétains ; (3)l’identification des processus qui contrôlent le devenir de ces éléments au cours du traitement.Les butylétains sont mesurés dans les matrices particulaires, dissoutes et dans les boues, par couplage GC-ICP-MS, dans toutes les étapes du traitement par lagunage de deux communes rurales du département de l’Hérault (34,France) : Gigean (6000 eq-hab.) et Montbazin (4500 eq-hab.). On montre que les trois espèces butylées sont systématiquement présentes dans tous les échantillons prélevés sur les deux STEP. Les butylétains arrivent principalement sous forme particulaire dans les eaux brutes en entrée des stations. Au cours du traitement, les processus de sorption sur les particules en suspension et la décantation de ces dernières au fond de chaque bassin sont les principaux facteurs permettant l’élimination des butylétains. Les premiers bassins anaérobies, de grande profondeur et de long temps de séjour, permettent l’élimination de plus de 60% à Gigean (93% à Montbazin) des butylétains. Les boues de fond de chaque bassin montrent des concentrations élevées en butylétains. La remise en suspension des butylétains est notée dans les derniers bassins de finition, peu profonds, ce qui peut être due à la re-stratification thermique. En sortie de station, malgré les abattements importants, des concentrations non négligeables en butylétains (12 à 228 et 1.8 à 15 ng(Sn).L-1 respectivement pour Montbazin et Gigean) sont rejetées dans le milieu récepteur. Des expériences de sorption basées sur la mise en contact de butylétains avec des boues de fond de bassin diluées ont été effectuées selon plusieurs approches expérimentales. On a ainsi montré que (1) la distribution des espèces MBT, DBT, TBT, entre les phases solide et liquide, est variable d’un test à l’autre selon les conditions opératoires ; (2) l’affinité entre les butylétains et la boue est importante, quelle que soit sa provenance. 98% des butylétains se retrouvent dans la phase solide, du fait de leur hydrophobicité. Le coefficient de distribution Kd entre le TBT et les boues est plus élevé que celui obtenu pour d’autres type de phases solides (75000 L.kg- 1) ; (3) le processus de sorption est rapide. De plus des processus de sorption, désorption et déalkylation du TBT, expliquant les variations des concentrations en MBT et DBT dans la phase solide ont été identifiés. La désorption du TBT est rapide. Il se dégrade dans la phase liquide en DBT dont une partie se transforme en MBT. La sorption du MBT sur les boues a été systématiquement mesurée. Le phénomène de sorption n’est donc pas complètement réversible au cours du temps. Ces résultats contribuent à expliquer les dysfonctionnements observés dans les stations de traitement par lagunage, par exemple lors d’apports directs d’eau de pluie.Cette thèse démontre la présence systématique des butylétains dans les stations d’épuration par lagunage naturel. Les données acquises in-situ couplées à des essais en laboratoire permettent de comprendre le comportement de ces composés lors de ce traitement : la fraction solide joue un rôle clé dans les processus de sorption-désorption-(bio)dégradation des butylétains. / This thesis deals with the behavior of a priority compound on the basis of the framework Directive on water at European level: tributyltin (TBT) ) and its metabolites (dibutyltin (DBT) and monobutyltin (MBT)). The study is focused on two waste stabilization pond treatment plants (WSP), which is an appropriate treatment to domestic effluents from sparsely urbanized areas.This thesis comes to fill the lack of scientific results on (1) the level of butyltin concentrations in domestic effluents from sparsely urbanized areas, in the input of the WSP and the output after treatment; (2) the efficiency of butyltins elimination by the WSP treatment; (3) the identification of the processes that control the fate of these elements during the treatment.Butyltins are measured in particulate and dissolved matrices and in sludge, by GC-ICP-MS, in all stages of the treatment by lagooning of two villages of the Department of Hérault (34, France): Gigean (6000 p.e.) and Montbazin (4500 p.e.).It is shown that the three butyltin species are consistently present in all samples taken from the two WSP. Butyltins arrive primarily in particulate form in the raw water. During treatment, the processes of sorption onto particulate matter and the settling of the latter at the bottom of each basin are the main factors for the elimination of butyltins. The first anaerobic ponds, characterized by deep depth and long residence times, allow the elimination of more than 60% Gigean (93% at Montbazin) of butyltins. Bottom sludge of each basin show high butyltins concentrations. The resuspension of butyltins is noted in the last maturation ponds, characterized by shallow depth, which may be due to re-thermal stratification. At the outlet, despite significant butyltin removal, concentrations in butyltins remain high (12 to 228 and 1.8 to 15 ng (Sn). L-1, respectively for Montbazin and Gigean).Laboratory batch experiments were conducted to study sorption processes following several experimental protocols. It was thus shown that: (1) the distribution of the butyltin species between solid and liquid phases is different from one test to another according to the operating conditions; (2) the affinity between butyltins and bottom sludge is important, regardless of its provenance. 98% of the butyltins are found in the solid phase, due to their hydrophobicity. The TBT sludge-water partition coefficient is higher than that obtained for other type of solid phases (75000 L.kg-1); (3) the process of sorption is fast.Moreover processes of sorption, desorption and dealkylation of TBT, explaining changes in concentrations of MBT and DBT in the solid phase were identified. Desorption of TBT is fast. It degrades in the liquid phase in DBT which part turns into MBT. The sorption of MBT on sludge has been systematically measured. Therefore, the sorption phenomenon is not completely reversible over time. These results help to explain the dysfunctions observed in WSP, for example after direct inputs of rainwater.This thesis shows the systematic presence of butyltin in waste stabilization pond treatment plants. In-situ data coupled with laboratory tests allow to understand the behaviour of these compounds during this treatment: the solid fraction plays a key role in the processes of sorption-desorption-(bio) degradation of butyltins.

Ce travail visait à évaluer le transport d’hydrocarbures aromatiques polycycliques (HAP) et de métaux dans des sols multi pollués, en s’intéressant plus particulièrement au couplage transport-réaction dans la zone non saturée du sol, selon deux axes de travail. En premier lieu, puisque de nombreux sites industriels sont multi pollués, nous avons choisi d’étudier l’influence des métaux sur la sorption des HAP et vice versa en système modèle. Nous avons montré que lors d’une pollution simultanée par du fluoranthène et du zinc, ce dernier est beaucoup moins retenu que lorsqu’il est présent seul et peut donc migrer plus facilement vers la nappe phréatique. Le plomb, quant à lui, est plus fortement retenu en présence de fluoranthène. En revanche, l’effet des métaux sur la rétention du fluoranthène est plus limité. En second lieu, nous avons évalué le transport des HAP et des métaux dans une terre d’une ancienne cokerie lorraine à plusieurs échelles : en colonne de laboratoire en conditions saturées et non saturées ainsi qu’en lysimètre de terrain, afin d’évaluer le pouvoir prédictif des sytèmes de laboratoire. Nous avons montré que les expériences en colonne de laboratoire surestiment la sortie des HAP telle qu’elle a lieu sur le terrain. En revanche, la sortie des métaux est bien prédite par de telles expériences. Mais le lysimètre ne peut pas être utilisé lors d’études de risque puisqu’il demande des durées d’expériences de plusieurs années afin d’avoir une vue globale des phénomènes qui s’y produisent. C’est pourquoi nous avons conçu un système original au laboratoire, capable d’évaluer leur transport conformément à ce qui se passe sur le terrain / PAHs and heavy metals are major soil pollutants and most of former industrial soils are co-polluted by both types of compounds. The aim of this work was to assess their transport in polluted soils under saturated and unsaturated flow conditions. This study was carried out by two approaches. First, heavy metal influence on PAH sorption and vice versa was studied with a “model” system. We showed that when the soil was simultaneously contaminated with fluoranthene and zinc, zinc retention was lower than when it was alone in the soil. As a consequence zinc would be expected to migrate more easily to the water table in co-polluted soils. Lead was more strongly retained in the presence of fluoranthene. But heavy metal influence on fluoranthene sorption was of minor importance. Then, PAH and heavy metal transport in a former coking plant soil was evaluated at the laboratory scale, under saturated and unsaturated flow conditions, by means of column experiments, and at the lysimeter scale under natural atmospheric conditions. The goal of these experiments was to compare PAH and heavy metal migration in a field-like situation with results obtained in the laboratory and to determine the appropriate experimental device for risk assessment studies. We showed that column experiments may overestimate PAH migration at the field scale. However heavy metal leaching was in accordance with what was expected from lysimeter experiments. But such experiments are rather time consuming and quite expensive, and as a consequence not adapted for risk assessment studies. Therefore we designed an original laboratory set up able to represent PAH and heavy metal migration at the field scale

No description available.

Ce travail vise à étudier le couplage entre écoulement et interactions physico-chimiques dans les sols, dans différentes conditions de saturation en eau, afin d’améliorer la prédiction du devenir des polluants. Il s’agit de comprendre en quoi le taux de saturation du milieu affecte la réactivité du sol vis-à-vis des polluants, et d’évaluer le pouvoir prédictif du transport de solutés réactifs étudié en milieu saturé sur la réactivité en conditions non saturées. Différents processus sont considérés : l’échange de cations calcium-zinc sur un milieu poreux modèle (sable-kaolinite), la sorption et désorption d’un composé organique sur une terre non contaminée, le transport de polluants prioritaires tels que les HAP sur une terre de friche industrielle. Dans chaque cas, des expériences en colonne de laboratoire ont été conduites en conditions d’écoulement saturé et non saturé permanent, permettant tout d’abord la caractérisation de l’hydrodynamique, puis l’étude du couplage avec la réactivité. Les courbes de percée obtenues ont été ensuite modélisées avec des codes tels que CXTFIT. On a montré l’influence de la teneur en eau du milieu sur le transport réactif, variable suivant le type de réaction considéré, la structure des milieux jouant également un rôle important. L’échange d’ions sur le milieu modèle n’est globalement pas affecté par la teneur en eau, dans une gamme proche de la saturation. En revanche, une plus forte sorption et une plus faible mobilisation des polluants organiques ont été observées en conditions non saturées. Le transport réactif de ces composés ne peut donc pas être prédit en conditions non saturées à partir de mesures en milieu saturé, qui peuvent surestimer le transport / The aim of this work was to study the link between water flow and physical and chemical interactions in soils under variably water flow conditions, in order to improve the prediction of contaminants fate. It deals with understanding how the porous media water content can modify soil reactivity towards contaminants, and assessing the possibility to predict reactivity under unsaturated conditions with reactive solute transport studied in saturated porous media. Various processes were considered: cations exchange calcium-zinc on a model porous media (sand-kaolinite), sorption and desorption of an organic compound on a non polluted soil, transport of priority contaminants such as PAHs on an industrial contaminated soil. In each case, experiments were carried out with soil columns at the laboratory scale under saturated and unsaturated steady-state flow conditions, in order to characterize at first hydrodynamics and then to study the link with reactivity. Modeling of the breakthrough curves was then performed with codes such as CXTFIT. We showed an influence of porous media water content on reactive transport which was different as a function of the interaction. Porous media structure must also be taken into account. Ions exchange on a model porous media was not globally modified by the water content varying in a range close to saturation. On the contrary, higher sorption and lower migration of organic contaminants were observed under unsaturated conditions. Reactive transport of these compounds cannot therefore be predicted under unsaturated conditions with tests performed on saturated porous media which may overestimate transport