A remoção da matéria orgânica biodegradável e não biodegradável presente em efluentes de branqueamento de polpa celulósica kraft foi investigado utilizando processos biológicos anaeróbios seguidos de processos de oxidação avançada (POA) baseados em ozônio. Os experimentos foram realizados utilizando-se efluentes da planta de branqueamento de polpa celulósica kraft de duas indústrias. O reator anaeróbio horizontal de leito fixo (RAHLF) em escala de bancada operou em regime contínuo durante 418 dias e o efluente biotratado era submetido à oxidação avançada aplicando ozônio e ozônio/UV em regime de batelada. Os resultados demonstraram que a sequência de tratamento Anaeróbio + POA baseados em ozônio, favoreceu satisfatoriamente a remoção da matéria orgânica (biodegradável e não biodegradável) presente no efluente de branqueamento de polpa celulósica Kraft, medida como DQO, COd, AOX, lignina solúvel em ácido (LSA), e valores da absorbância em comprimentos de onda na região UV-VIS do espectro (UV215, UV254, UV280, VIS346).Verificou-se com testes de ecotoxicologia aquática utilizando Daphnia similis e Ceriodaphnia sp, que os efluentes de branqueamento são tóxicos aos organismos aquáticos. Do mesmo modo, ensaios de genotoxicidade utilizando células da região meristemática da raiz do Allium cepa L (cebola comum), revelaram que esses efluentes apresentam atividade mutagênica, genotoxica e citotóxica. No entanto, observou-se que tantos os efeitos tóxicos bem como os genotóxicos e mutagênicos, estão estreitamente relacionados com o conteúdo da matéria orgânica biodegradável, uma vez que, após o processo anaeróbio apresentaram-se remoções estatisticamente significativas para todos os efeitos já mencionados (até 100%) com concomitante remoção da demanda química de oxigênio (até 55 \'+ OU -\' 9%) e do carbono orgânico dissolvido (até 57 \'+ OU -\' 7%). Ainda, verificou-se que após a aplicação do ozônio/UV, embora, o teste de biodegradabilidade aeróbia pelo método de Zahn Wellens revelasse que esse efluente era o mais biodegradável, tanto a toxicidade crônica como a genotoxicidade e a citotoxicidade resultaram estatisticamente significativas em relação ao controle negativo. Este resultado indica que, efetivamente a matéria orgânica biodegradável deset tipo de efluentes pode se relacionar com a presença de efeitos tóxicos e genotóxicos. Tal fato não foi verificado no caso do tratamento apenas com ozônio. / Removal of biodegradable and non biodegradable organic matter present in kraft pulp mill effluent was investigated integrating an anaerobic biological process and advanced oxidation processes based on ozone. The experiments were carried out using two different Brazilian pulp mill. The bench scale Horizontal Anaerobic Immobilized Sludge Bioreactor (HAIS) was operated during 418 days; subsequently the biotreated effluent was oxidized applying ozone and ozone/UV in batch regime. The results show that the treatment sequence, anaerobic process + advanced oxidation processes based on ozone, results in removal of both organic matter biodegradable and non-biodegradable measured as chemical oxidation demand (COD), dissolved organic carbon (COd), adsorbable organic halides (AOX), acid soluble lignin (ASL) and absorbance values in the UV-VIS spectrum (i.e. UV215, UV205, UV280, VIS346). Ecotoxicological tests using Daphnia similis and Ceriodaphnia sp. confirmed that bleached kraft pulp mill is toxic to aquatic organisms. Moreover, genotoxicity tests with meristematic cells of Allium cepa (i.e. common onion) roots show that this type of effluent results in mutagenic, genotoxicological and citotoxicological activities. It is to be highlighted however that both toxicological and genotoxicological effects are closely related to the biodegradable organic matter, thus, after the anaerobic processes the removal of these effects occur, concomitant to reductions is chemical oxygen demand (55 \'+ OU -\' 9%) and dissolved organic carbon (57 \'+ OU -\' 7%). It was also observed that after ozone/UV application, both the chronic toxicity and genotoxicity activity were statically significant if compared with the negative control, although the Zahn Wellens test revealed that this effluent had the highest biodegradability. These results confirmed that biodegradable organic matter could be related with toxic and genotoxic effects. In the case of ozone application alone this behavior was not observed.

A remoção da matéria orgânica biodegradável e não biodegradável presente em efluentes de branqueamento de polpa celulósica kraft foi investigado utilizando processos biológicos anaeróbios seguidos de processos de oxidação avançada (POA) baseados em ozônio. Os experimentos foram realizados utilizando-se efluentes da planta de branqueamento de polpa celulósica kraft de duas indústrias. O reator anaeróbio horizontal de leito fixo (RAHLF) em escala de bancada operou em regime contínuo durante 418 dias e o efluente biotratado era submetido à oxidação avançada aplicando ozônio e ozônio/UV em regime de batelada. Os resultados demonstraram que a sequência de tratamento Anaeróbio + POA baseados em ozônio, favoreceu satisfatoriamente a remoção da matéria orgânica (biodegradável e não biodegradável) presente no efluente de branqueamento de polpa celulósica Kraft, medida como DQO, COd, AOX, lignina solúvel em ácido (LSA), e valores da absorbância em comprimentos de onda na região UV-VIS do espectro (UV215, UV254, UV280, VIS346).Verificou-se com testes de ecotoxicologia aquática utilizando Daphnia similis e Ceriodaphnia sp, que os efluentes de branqueamento são tóxicos aos organismos aquáticos. Do mesmo modo, ensaios de genotoxicidade utilizando células da região meristemática da raiz do Allium cepa L (cebola comum), revelaram que esses efluentes apresentam atividade mutagênica, genotoxica e citotóxica. No entanto, observou-se que tantos os efeitos tóxicos bem como os genotóxicos e mutagênicos, estão estreitamente relacionados com o conteúdo da matéria orgânica biodegradável, uma vez que, após o processo anaeróbio apresentaram-se remoções estatisticamente significativas para todos os efeitos já mencionados (até 100%) com concomitante remoção da demanda química de oxigênio (até 55 \'+ OU -\' 9%) e do carbono orgânico dissolvido (até 57 \'+ OU -\' 7%). Ainda, verificou-se que após a aplicação do ozônio/UV, embora, o teste de biodegradabilidade aeróbia pelo método de Zahn Wellens revelasse que esse efluente era o mais biodegradável, tanto a toxicidade crônica como a genotoxicidade e a citotoxicidade resultaram estatisticamente significativas em relação ao controle negativo. Este resultado indica que, efetivamente a matéria orgânica biodegradável deset tipo de efluentes pode se relacionar com a presença de efeitos tóxicos e genotóxicos. Tal fato não foi verificado no caso do tratamento apenas com ozônio. / Removal of biodegradable and non biodegradable organic matter present in kraft pulp mill effluent was investigated integrating an anaerobic biological process and advanced oxidation processes based on ozone. The experiments were carried out using two different Brazilian pulp mill. The bench scale Horizontal Anaerobic Immobilized Sludge Bioreactor (HAIS) was operated during 418 days; subsequently the biotreated effluent was oxidized applying ozone and ozone/UV in batch regime. The results show that the treatment sequence, anaerobic process + advanced oxidation processes based on ozone, results in removal of both organic matter biodegradable and non-biodegradable measured as chemical oxidation demand (COD), dissolved organic carbon (COd), adsorbable organic halides (AOX), acid soluble lignin (ASL) and absorbance values in the UV-VIS spectrum (i.e. UV215, UV205, UV280, VIS346). Ecotoxicological tests using Daphnia similis and Ceriodaphnia sp. confirmed that bleached kraft pulp mill is toxic to aquatic organisms. Moreover, genotoxicity tests with meristematic cells of Allium cepa (i.e. common onion) roots show that this type of effluent results in mutagenic, genotoxicological and citotoxicological activities. It is to be highlighted however that both toxicological and genotoxicological effects are closely related to the biodegradable organic matter, thus, after the anaerobic processes the removal of these effects occur, concomitant to reductions is chemical oxygen demand (55 \'+ OU -\' 9%) and dissolved organic carbon (57 \'+ OU -\' 7%). It was also observed that after ozone/UV application, both the chronic toxicity and genotoxicity activity were statically significant if compared with the negative control, although the Zahn Wellens test revealed that this effluent had the highest biodegradability. These results confirmed that biodegradable organic matter could be related with toxic and genotoxic effects. In the case of ozone application alone this behavior was not observed.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A FotossÃntese e a respiraÃÃo sÃo bem conhecidos como sendo responsÃveis pela produÃÃo de energia no interior das cÃlulas de plantas. Acoplados à estes processos bioenergÃticos, a transferÃncia de elÃtrons que ocorre nas membranas do cloroplasto e mitocÃndria, tambÃm sÃo considerados com tendo potencial de produÃÃo de ROS. PossÃveis interaÃÃes no funcionamento dessas organelas permanecem pouco conhecidas, especialmente em resposta a condiÃÃes de estresse. Sob estas condiÃÃes, sugere-se que as vias de transferÃncia de elÃtrons ligadas à AOX, à pUCP ou à PTOX poderia limitar a formaÃÃo de ROS reduzindo assim danos oxidativos Ãs organelas celulares. Em nosso trabalho, foram selecionadas duas cultivares de Vigna unguiculata, inicialmente caracterizados como sensÃvel (cv 1183) ou tolerante (cv EPACE1) à seca. Sob condiÃÃes experimentais, as duas cultivares nÃo apresentaram diferenÃas significativas na sensibilidade à seca. Entretanto o cultivar EAPCE1 foi mais tolerante ao ozÃnio com base no desenvolvimento de necrose e de vÃrios parÃmetros fisiolÃgicos (ϕPSII) e bioquÃmicos (teor de glutationa). Para os perfis de expressÃo de genes que codificam AOX, PUCP e PTOX duas respostas foram claramente identificadas no cultivar EPACE1. Em um tempo curto, a expressÃo destas proteÃnas à geralmente estimulada. Em um perÃodo mais longo (14 dias), a resposta à diferente, dependendo da tipo de estresse. Sob o ozÃnio, um aumento da expressÃo das proteÃnas mitocondriais à mantida enquanto o gene que codifica para a PTOX à sub-regulada. Sob seca a proteÃna desacopladora do plastÃdio (PTOX) à superexpressa. Sob condiÃÃes de combinaÃÃo stress, seca combinada com ozÃnio, o efeito da seca sobre o fluxo de ozÃnio nas folhas nÃo foi alterado, e os genes VuPTOX e VuUCP1b sÃo super-expressos depois de 3 e 7 dias de stress. Este aumento da expressÃo, jà observado em resposta à seca por aplicada separadamente poderia desempenhar um papel na prevenÃÃo da formaÃÃo de ROS tanto em mitocÃndrias e cloroplastos prevenindo assim os danos causados pelo ozÃnio. / Possible interactions between chloroplast and mitochondria remain poorly known, particularly in response to stress conditions. Under these conditions, it is suggested that the electron transfer pathways linked to AOX or pUCP (mitochondrial uncoupling proteins) and PTOX (plastidial uncoupling protein) could limit the formation of ROS to reduce oxidative damage in cellular organelles. In our work, we selected two cultivars of Vigna unguiculata, cv 1183 and cv EPACE. Under our experimental conditions, both cultivars showed no real differences in sensitivity to drought. However cv EPACE was more tolerant to O3 based on the development of necrosis and several physiological parameters (Fv/Fm, ϕPSII) and biochemical (glutathione content). For the expression profiles of genes encoding AOX, PUCP and PTOX two responses were clearly identified in the cultivar EPACE. On a shortterm, expression of these proteins is generally stimulated. On a longer term (14 days), the answer differs depending on the treatment. Under O3, the strongest expression of mitochondrial proteins is maintained while the gene encoding the PTOX is own-regulated. Under drought only the plastid protein (PTOX) is upregulated. Under conditions of stress combination, drought has little effect on the influx of O3 in the leaves, and the VuPTOX and VuUCP1b genes are up-regulated after 3 and 7 days of stress. This ver-regulation, already observed in response to drought alone could play a role in preventing the formation of ROS in both mitochondria and chloroplasts.

Ce travail a été consacré à l'étude des sous-produits de désinfection formés lors de la chloration des eaux de piscine publiques. En effet, parallèlement à son action désinfectante, le chlore réagit sur les composés organiques et minéraux introduits dans l'eau des bassins par les baigneurs (urine, sueur, ...) pour former des sous-produits indésirables (chloramines et composés organohalogénés).Des analyses d'urée, principal composé précurseur de chloramines inorganiques, ont été effectuées dans une cinquantaine d'eaux de piscine. Les concentrations mesurées ont été comprises entre 0,14 et 3,67 mg/L (valeur moyenne : 1,08 mg/L ; écart-type : 0,70 mg/L). L'étude de la réactivité du chlore sur l'urée (cinétique et consommation de chlore) effectuée sous différentes conditions expérimentales a mis en évidence une très grande stabilité de l'urée en présence de chlore libre dans les eaux de piscines.Les analyses de sous-produits de chloration ont démontré que l'hydrate de chloral représente l'un des sous-produits de chloration majoritaire avec les acides dichloroacétique et trichloroacétique. Cette étude a aussi permis de déterminer la constante cinétique d'hydrolyse de l'hydrate de chloral dans l'eau, l'influence du pH et de la température sur la vitesse d'hydrolyse, ainsi que les potentiels de formation d'hydrate de chloral à partir de quelques constituants de l'urine.La dernière partie de ce travail a porté sur l'étude de la réactivité de l'ozone sur le chlore et sur des sous-produits de chloration ainsi que sur l'étude de l'incidence d'une préozonation des eaux de piscines (en absence et en présence de chlore libre) sur la formation des sous-produits organohalogénés lors d'une post-chloration. / The aim of this work was to study of the formation of disinfection by-products during the chlorination of public swimming pools water. In parallel to its disinfecting action, chlorine reacts with organic and inorganic compounds introduced into the swimming pool water by bathers (urine, sweat, ...) to form undesirable by-products (chloramines and organohalogenated matters).A statistical study of the presence of urea, the major component of urine and sweat, and the main precursor compound of inorganic chloramines, in public swimming poolwater has been made. Measured concentrations were between 0.14 and 3.67 mg/L (mean value: 1.08 mg/L, s.d: 0.70 mg/L). The study of the reactivity of chlorine with urea (kinetic and chlorine consumption) made under different experimental conditions, showed a very high stability of urea in the presence of free chlorine in the pools water.Analysis of chlorination by-products showed that chloral hydrate, with the dichloro and the trichloroacetic acids, is one of the major chlorination by-products found. This study also determined the kinetic rate constant of hydrolysis of chloral hydrate in water, the influence of the pH and the temperature on the rate of hydrolysis and the potential of chloral hydrate formation from some constituents of the urine.The last part of this work was focused on the study of the reactivity of ozone on chlorine and some disinfection by-products, as well as the study of the impact of preozonation of swimming pools water (in absence and presence of free chlorine) on the formation of organohalogenated by-products during a post-chlorination.

In this study, effects of different carbon sources and their feeding strategies on recombinant human growth hormone (rhGH) production by Pichia pastoris were investigated by means of cell growth, recombinant protein production and expression levels of hGH and alcohol oxidase (AOX) genes. In this content, firstly, the strain to be used for high level rhGH production was selected between the two phenotypes, i.e., P. pastoris hGH-Mut+ and P. pastoris hGH-MutS. In this selection both phenotypes were compared in two different media containing glycerol/methanol or sorbitol/methanol and P. pastoris-hGH-Mut+ strain grown on medium containing 30 g/L sorbitol with 1% (v/v) methanol was found to have the highest hGH expression level and rhGH production level, 9.84x109 copies/mg CDW and 120 mg/L, respectively. Thereafter, effects of sorbitol, mannitol, fructose, lactose, sucrose, citric acid, lactic acid and acetic acid were investigated by using P. pastoris hGH-Mut+ strain in laboratory scale bioreactors. Among them sorbitol and sucrose were selected to be compared for production in pilot scale bioreactors by adding them batch-wise at the beginning of induction phase with fed batch methanol feeding scheme at &amp / #956 / =0.03h-1. It was shown that sucrose does not support cell growth as sorbitol although it does not repress recombinant protein production. Then three different feeding strategies were applied to develop sorbitol/methanol mixed feeding i) single sorbitol addition at t=0, ii) besides at t=0, adding second batch-wise sorbitol at t=9 h, iii) giving pulse methanol at t=24 h to trigger AOX promoter. These three strategies were compared with a production without addition of co-substrate sorbitol. Substrate consumption, cell growth, recombinant protein production and expression levels of hGH and AOX were investigated for these different feeding strategies. The highest cell concentration was achieved in third strategy as 55 g/L where the highest extracellular rhGH production (301 mg/L) was achieved in the second strategy, with addition of two times of sorbitol. For this highest recombinant protein production case, overall cell and product yield on total substrate were found as 0.17 g/g and 1.71 mg/g, respectively. Moreover, the highest hGH and AOX expression levels were obtained in this strategy.

Le champignon filamenteux Podospora anserina constitue un système modèle pour l'étude de plusieurs processus biologiques, notamment le vieillissement. Une relation de causalité entre le fonctionnement de la chaine respiratoire et la longévité a été établie pour la première fois chez P. anserina et cette relation de causalité semble conservée. Le lien entre fonctionnement de la chaîne respiratoire et longévité pourrait se faire en partie par l'induction d'une régulation rétrograde en réponse à un dysfonctionnement mitochondrial. Les études des régulations rétrogrades mitochondriales et chloroplastiques montrent qu'en réponse à un dysfonctionnement de ces organites, il y a une reprogrammation de l'expression génique qui participe à la plasticité adaptative des espèces en réponse à l'environnement. Un gène cible d'une régulation rétrograde mitochondriale a été identifié chez P. anserina: le gène aox. L'oxydase alternative appartient à une voie respiratoire alternative en conditions de dysfonctionnement de la voie des cytochromes. Deux facteurs de transcription acteurs de cette régulation rétrograde mitochondriale ont été identifiés par une approche génétique. Ces protéines, RSE2 et RSE3, appartiennent à la famille des protéines Zn2Cys6 et sont les régulateurs majeurs du gène aox. Outre le gène aox, ces deux facteurs de transcription corégulent les deux enzymes de la néoglucogenèse FBP (Fructose-1,6-biphosphatase) et PCK (Phosphoénolpyruvate carboxykinase). Des allèles gain de fonction des gènes rse2 et rse3 ont été isolés et le crible pratiquement saturé. L'analyse de ces mutations ainsi que des approches de mutagenèse dirigée, ont permis de proposer l'existence de régions régulatrices dans les séquences protéiques RSE2 et RSE3. Une approche transcriptomique a permis d'identifier de nouvelles cibles de RSE2 et RSE3 activées lors d'un dysfonctionnement mitochondrial : le gène fhb (codant une flavohémoglobine) et le gène Pa_6_4030 (codant une α/β hydrolase). Une approche métabolomique a permis une meilleure compréhension de la reprogrammation métabolique en réponse à un dysfonctionnement de la chaîne respiratoire et du rôle de RSE2/RSE3 dans cette reprogrammation.RSE2 et RSE3 sont donc des acteurs d'une régulation rétrograde mitochondriale responsables de l'activation de voies respiratoires alternatives mais aussi d'une reprogrammation du métabolisme de P. anserina qui permettrait de maintenir une homéostasie cellulaire en condition de dysfonctionnement mitochondrial.

Organohalogen compounds are formed in swimming pool waters when natural organic matter, such as hair, urine or sweat etc., react with the used disinfectant (usually chlorine). Many of the organohalogen compounds are persistent and hazardous for human health and aquatic ecosystems. Backwash water from swimming pool facilities is often released to the sewer and contain these compounds. The connected wastewater treatment plant receives this water, where some of these compounds escapes the treatment process, into the recipient. It is therefore important to minimize the levels of organohalogen compounds in the influent water to the wastewater treatment plant. In this study, potential treatment techniques for organohalogen compounds at the swimming pool facility have been investigated. The main focus have been on an experimental column test with four filter materials applied (granular activated carbon, natural zeolites, PoloniteR and Zugol). Real backwash water was used. Furthermore, other techniques have been theoretically investigated as well. The activated carbon directly showed the most efficient removal efficiency (above 95 %), but all filter materials had a removal to a certain degree and became more efficient by time. The results further suggest that the more lipophilic organohalogen compounds are bound to particulate matter and highly affected by physical filtration. Another important conclusion is that the specific activated carbon used in the study is not suitable for the purpose, because it released very high levels of phosphorus in the beginning of the column test as well as showing some practical problems. However, other types of activated carbon exists. Next step recommended is to determine the lifetime of the filters. / När människor badar i bassänger hamnar vanligtvis naturligt organiskt material i dem, såsom urin, svett, hår och hudflagor. Desinfektionsmedlet som tillsätts (oftast klor) har som syfte att avlägsna mikroorganismer, men när naturligt organiskt material hamnar i vattnet kommer också oavsiktliga reaktioner ske och halogenerade organiska föreningar bildas. Dessa föreningar kan kvantifieras via AOX måttet (adsorberbar organisk halogen), vilket är den samlade förekomsten av alla bundna organiska halogener i ett prov. AOX består således av flera hundra olika föreningar, varav vissa är mer lipofila och benämns EOX (extraherbar organisk halogen). Många av de föreningar inkluderade i AOX är bioackumulativa, persistenta och giftiga för akvatiska organismer, även i låga koncentrationer. Förutom att vara miljöfarliga för akvatiska ekosystem, kan de också vara skadliga för människans hälsa. Filtret som renar badvattnet i simhallar behöver backspolas regelbundet och backspolvattnet, som innehåller AOX, skickas vanligen till spillvattennätet. Vid avloppsreningsverket är det visat i ett tidigare examensarbete samt i andra rapporter att en del av de inkommande AOX ämnena även följer med det utgående, renade, vattnet ut i recipienten. Det är därmed av vikt att minimera ämnena redan vid källan, det vill säga på badanläggningen. I denna masteruppsats har behandlingstekniker för halogenerade organiska föreningar undersökts. Huvudfokus har varit på experimentella kolonntester för fyra filtermaterial (granulerat aktivt kol, naturliga zeoliter, PoloniteR och Zugol), men även andra tekniker har studerats teoretiskt. I testerna användes äkta backspolvatten från en simhall. Alla material reducerade AOX till viss del och visade på effektivare reducering efter hand. Det var dock tydligt att det aktiva kolet var mest effektivt och hade hög reducering redan i första mätningen, AOX-reduceringen låg på över 95 % (jämfört med det obehandlade backspolvattnet). Vad som dock var problematiskt med det aktiva kolet var att det släppte höga halter fosfor i början av kolonntestet, vilket också bekräftades med ett skaktest. Dessutom uppvisade materialet praktiska problem. Ur ett realistiskt perspektiv med dessa problem i åtanke, blir det inte hållbart i längden att använda detta specifika kol. Det finns dock många olika typer av aktivt kol, vilka förmodligen är mer lämpliga och som inte uppvisar dessa problem, och kan användas för detta ändamål. Vidare antyder det erhållna resultatet att de mer lipofila föreningarna av AOX (EOX) är bundet till partikulärt organiskt material och därmed påverkas väsentligt av mekanisk filtrering. Det är dock viktigt med en aktiv bindning. Projektet har påverkats av covid-19 pandemin med lägre antal folk på badhusen samt mindre tillgång till laboratoriet vid KTH. En föreslagen förbättring av metoden är att ha en kontinuerlig omblandning i förvaringskärlet med det obehandlade vattnet innan det tillförs kolonnerna. Vidare nämns det att modifierade zeoliter verkar lovande samt att nästa viktiga steg för projektet är att bestämma livstiden för filtermaterialen.

The aim of this work is to contribute to the process development of the ECF light bleaching sequence Q(OP)D(PO) by providing a better understanding of the bleaching of softwood kraft pulp. There are few published studies on this type of sequence, and more knowledge is needed on how to reduce environmental impact, improve cost-effectiveness and ensure a high pulp quality. Firstly, this research showed that using a pH buffer to stabilize the pH at a near-neutral level during bleaching with chlorine dioxide can lower the formation of adsorbable organically bound halogens (AOX) without altering the bleaching efficiency. A near-neutral pH decreases the formation of strongly chlorinating species so that the AOX content in the bleaching effluents is reduced by up to 30%. The increased pH in the near-neutral pH D stage compared with the reference lowered the chlorine dioxide consumption, resulting in a higher kappa number and viscosity. A lower degradation of hexenuronic acid correlated well with a lower AOX content in the effluents, affirming earlier theories that hexenuronic acid has an important impact on AOX formation. Secondly, this research aimed at studying bleachability in (OO)Q(OP)D(PO). The bleachability was defined as delignifying and brightness gain bleachability, which is suited to ECF light bleaching sequences. The delignifying and brightness gain bleachability were used to evaluate the stages in (OO)Q(OP)D(PO) in regard to the unbleached kappa number. When comparing different stages, it is possible to distinguish the bleaching efficiency in each stage. For this ECF light sequence, the bleachability depends on the purpose of the stage. It was found that in the stages that are mainly delignifying (OO and D), a higher unbleached kappa number is beneficial for the delignifying bleachability, although the brightness gain is not improved. However, in the stages that are mainly brightness increasing (OP and PO), the brightness gain bleachability is improved by a lower unbleached kappa number. Thirdly, the bleaching of the pulp samples in this study with the ECF light sequence was most effective with a kappa number around 32 after cooking. Although an even higher kappa number resulted in a higher yield after cooking, it seemed that this bleaching sequence cannot preserve the yield gain. Kappa number 32 also gave the best results in regard to brightness ceiling and viscosity. On the other hand, kappa number 27 was the most favourable with regard to yellowing and chemical charge. / <p>Examinator: Helena Håkansson, lektor, Karlstads universitet</p>

Spridning av läkemedelsrester och andra prioriterade mikroföroreningar i miljön har uppmärksammats och stor oro väckts kring problematiken. Bland observationer som forskare har noterat till följd av antibiotika, hormoner och läkemedel i vattenmiljöer är bland annat bakteriell resistens, könsbyte och sterilitet hos fisk och groddjur. Persistenta föroreningar som per- och polyfluor alkalysyror (PFAS) bryts inte heller ner i naturen och mikroskräppartiklar kan anrikas i vattendrag och orsaka negativa effekter på vattenlevande organismer. Gemensamt för mikroföroreningar är att dessa förekommer oftast i små halter och kan härstamma från olika mänskliga aktiviteter. Avloppsreningsverk (ARV) är inte primärt anpassade för att avskilja mikroföroreningar utan främst för att avlägsna kväve, fosfor och organiskt material. Uppströmsarbete är inte heller tillräckligt effektivt för att avlasta reningsprocessen vilket medför att mängden mikroföroreningar ökar i vattenmiljöer och sätter ytterligare påtryckningar på ARV. Utmaningar som ARV står inför idag med nya mikroföroreningar och förekomsten av dessa i miljön har väckt frågor både nationellt och internationellt. Stockholm Vatten och Avfalls (SVOA) beslut att implementera membranbioreaktor (MBR) på Henriksdals reningsverk av porstorleken 0,04 μm är en åtgärd för att rusta upp inför framtida hydrauliska volymer men även potentiella striktare reningskrav. Fördelen med MBR-processen är att den förhindrar föroreningar som förekommer partikulärt att passera membranen och på så sätt hindras skadliga ämnen att passera reningsprocessen. I dagsläge saknas krav på ARV att rena avloppsvatten från de flesta mikroföroreningar. Det förväntas dock att kommande lagstiftning omfattar läkemedel och andra organiska föroreningar. I detta projekt undersöktes mikroföroreningar i form av läkemedelsrester, antibiotika, hormoner, PFAS och mikroskärp i en MBR-process samt förekomsten av adsorberbara och extraherbara organiska halogener (AOX, EOX) som potentiellt bildas under rengöring av membranen till följd av reningsprocessen. Resultat från detta projekt med MBR-processen visade en generell högre reduktion av prioriterade mikroföroreningar i avloppsvatten än tidigare undersökningar på konventionella ARV, med undantag för några substanser som visade på en liknande sämre reduktion. Läkemedlen diklofenak, oxazepam, citalopram med flera visade på en sämre reduktion och lika så för antibiotikumen clindamycin, claritomycin och erytromycin där reduktionen var negativ och visade på en återkommande trend. Östrogena hormoner reducerades i reningsprocessen och likaså för mikroskräp där 60 partiklar/m3 mikroplast av porstorleken större än 300 μm passerade membranen. Mikroplast av en porstorlek i intervallet mindre än 300 men större än 50 μm passerade 140 partiklar/m3 membranen. För AOX och EOX var halten i MBR-processen typiska och i nivå med tidigare undersökningar genomförda på konventionella ARV. Eftersom membranen inte kan avskilja partiklar på molekylnivå visades sig även att det passerade fortfarande mikroföroreningar som undersöktes. En slutsats från detta projekt är att endast ett få tal ämnen reducerades helt medan majoriteten av de prioriterade mikroföroreningarna reducerades delvis i avloppsvatten. För att kunna reducera dessa prioriterade mikroföroreningar i reningsprocessen ytterligare om striktare reningskrav skulle bli aktuella krävs vidare efterbehandling efter MBR-processen. / Release of pharmaceutical residues and other emerging substances in the environment has been highlighted and raised a great concern regarding the issue. Among observations that scientists have noted as a result of antibiotics, hormones and pharmaceutical residues in the aquatic environment are bacterial resistance, sex change and sterility in fish and batrachians. Persistent pollutants such as perfluorinated-alkylated substances (PFAS) are also not degraded in nature, and microscopic debris particles can be enriched in aquatic systems and cause adverse effects on aquatic organisms. The common aspect with these substances is that they usually occur in small quantities and can derive from different human activities. Wastewater treatment plants (WWTP) are not primarily designed to separate emerging substances of concern (ESOC), but primarily to remove nitrogen, phosphorus and particulate organic matter. Upstream work is also not sufficiently effective to relieve the purification process, which means that the amount of pollutants increases in aquatic environments and puts additional pressure on the WWTP. The challenges facing WWTP today with ESOC and their presence in the environment has raised issues both nationally and internationally. Stockholm Vatten och Avfall (SVOA) decision to implement a membrane bioreactor (MBR) with poresize of 0,04 μm at Henriksdal WWTP is a step to prepare for future hydraulic volumes, but also potentially stricter treatments requirements regarding ESOC. The advantage of the MBR process is that it prevents contaminants that appear to be particulate to pass the membranes and end up in the receiving waters. Today, WWTP are not required to treat wastewater in order to remove pharmaceutical residues, antibiotics, hormones, PFAS or microscopic debris particles. However, it is expected that future legislations will include pharmaceuticals and other organic pollutants. In this project, ESOC such as pharmaceutical residues, antibiotics, hormones, PFAS and microscopic debris in the MBR-process are studied as well as the presence of adsorbable and extractable organic halogens (AOX, EOX) that are possibly formed during the cleaning or maintains of the membranes. Results from this study showed a higher general reduction of the studied ESOCs in wastewater with the MBR-process than previous studies in conventional WWTP, except of some substances that showed a poor reduction. Pharmaceuticals such as diclofenac, oxazepam and citalopram showed a weak reduction as well as the antibiotics clindamycin, clarithromycin and erythromycin where they showed a higher outcome levels than the incoming to the treatment process. Estrogenic hormones were reduced in the purification process as well as microplastics where only 60 particles/m3 of pore size higher than 300 μm passed the membranes. Microplastics of the pore size smaller than 300 and larger than 50 μm were detected to 140 particle/m3 in the effluent water. For AOX and EOX, the level of MBR process showed typical values and were in line with previous studies on conventional ARV. However, since the membranes cannot treat contaminants at molecular level, it was also shown that some ESOC that were studied bypassed the treatment process. A conclusion from this project is that only a few numbers of substances were fully reduced while the majority of ESOCs were partially reduced in wastewater. In order to reduce further ESOCs and in case of stricter treatment were to be applied, additional post-treatment is also needed for the MBR process.