Per- and polyfluoroalkyl substances (PFASs) are man-made substances that hold unique properties. They are not only oil- and water repellants but also very resistant to degradation. Due to these properties, the applications are endless and PFASs can be found in a wide range of industrial applications and commercial products. The effluents of wastewater treatment plants (WWTPs) have been pointed out as one of the major sources of PFASs in the environment. The main aim of this project was to evaluate the sources and the occurrence of PFASs in a wastewater network in a Swedish city and in the different treatment steps at the connected WWTP. Another objective was to use these data to calculate mass flows and to investigate the fate of PFASs within the WWTP. The city of Uppsala and the WWTP Kungsängsverket were selected as study objects. Both wastewater and sludge were sampled and analyzed. In the wastewater network, a total of 15 pumping stations (PSTs) were sampled for wastewater, and at the WWTP, a total of 10 wastewater and 10 sludge samples were taken. The samples consisted of grab samples (n = 24), time-integrated samples (100 mL every 20 min during 24 hours, n = 2) and flow proportional samples (24 hours, n = 9). The aqueous and sludge samples were prepared for analysis using solid-phase and solid liquid extraction, respectively, and then analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). The PFAS concentrations and composition profiles varied greatly in the network. High concentrations of 6:2 fluorotelomer sulfonate (6:2 FTSA) were generally found in the wastewater, which indicates increased usage of 6:2 FTSA in industrial processes and applications as replacement for perfluorooctane sulfonate (PFOS) and/or leaching from fire-training sites. A hot spot was detected (Sågargatan PST: ΣPFAS = 55,000 ng L-1 = 110,000 mg d-1) with elevated discharges of C3 – C8 perfluoroalkyl carboxylates (PFCAs). The studied WWTP was ineffective in removing C4, C6, C8 perfluoroalkyl sulfonates (PFSAs), C3 – C8 PFCAs and 6:2 FTSA from wastewater. Longer chained C9 – C17 PFCAs tended to partition to sludge more effectively than shorter chained C3 – C8 PFCAs, where PFCAs with an even amount of perfluorated carbon atoms had a higher affinity for sludge than those with an odd amount. The PFAS concentrations and mass flows tended to increase across the second clarifier in both wastewater and sludge, probably due to precursor degradation. PFSAs and PFCAs tended to be at similar or lower concentrations in the effluent compared to the influent. This shows that these substances enter the WWTP from an upstream source and are not formed or added in the WWTP. The transformation of precursors is therefore not the most important source of PFASs in Kungsängsverket. PFASs in wastewater at a large scale municipal WWTP may origin to a large extent from both industrial applications and domestic sources, such as daily life products. The new knowledge generated within this project will help Uppsala Vatten to protect drinking water supplies and the receiving aquatic environment from PFAS contamination. / Per- och polyfluoroalkylerade substanser (PFAS) är konstgjorda ämnen som har unika egenskaper. De är inte bara fett- och vattenavvisande utan är även mycket resistenta mot nedbrytning. På grund av dessa egenskaper är applikationerna med PFAS oändliga, och de används i en lång rad industriella applikationer och kommersiella produkter. Renat vatten från avloppsreningsverk har pekats ut som en av de största källorna av PFAS i miljön. Syftet med det här projektet var att undersöka källorna och uppkomsten av PFAS i ett ledningsnät i en svensk stad och även före/efter de olika reningsstegen i det största reningsverket. Ett annat mål var att använda dessa data för att beräkna massflöden och att studera ödet för PFAS i reningsverket. Uppsala stad och reningsverket Kungsängsverket valdes som studieobjekt. Både avloppsvatten och slam provtogs och analyserades. I ledningsnätet provtogs totalt 15 pumpstationer (PST) med avseende på avloppsvatten och i reningsverket togs det totalt 10 avloppsvatten- och 10 slamprover. Proverna bestod av stickprover (n = 24), tidsintegrerade prover (100 mL var 20 min under 24 timmar, n = 2) och flödesproportionerliga prov (24 timmar, n = 9). Vatten- och slamproverna preparerades för analys med hjälp av fastfas- respektive fast-vätske-extraktion, och analyserades därefter med vätskekromatografi kopplat till tandem-mass-spektrometri (LC/MS/MS). PFAS koncentrationerna och sammansättningsprofilerna varierade mycket i ledningsnätet. Koncentrationerna av 6:2 fluorotelomersulfonsyra (6:2 FTSA) var generellt höga i avloppsvattnet, vilket tyder på en ökad användning av 6:2 FTSA i industriella processer och applikationer som ersättningssubstans för perfluorooktansulfonsyra (PFOS) och/eller urlakning från brandövningsplatser. En så kallad hot spot detekterades i ledningsnätet (Sågargatan PST: ΣPFAS = 55 000 ng L-1 = 110 000 mg d-1) med punktutsläpp av C3 – C8 perfluoroalkylerade karboxylsyror (PFCA). Det studerade reningsverket var inte effektivt för rening av C4, C6, C8 perfluoroalkyl-sulfonsyror (PFSAs), C3 – C8 PFCAs och 6:2 FTSA. PFAS av typen C9 – C17 PFCA (långa kolkedjor) tenderade att fördela sig till slamfasen mer än C3 – C8 PFCA (kortare kedjor), där PFCA med ett jämnt antal perfluorerade kolatomer hade större affinitet för slam än de med udda. PFAS koncentrationerna och massflödena tenderade att öka från första till andra sedimentations-tanken, både i avloppsvatten och i slam, troligtvis som en följd av degradering av prekursorer. PFSA och PFCA tenderade att ha likvärdiga eller lägre koncentrationer i ut- jämfört med inflöde. Detta tyder på att huvudkällorna för dessa substanser i avloppsvatten finns uppströms och uppkommer inte genom bildning eller tillsats i reningsverket. Nedbrytning av prekursorer är därför inte den viktigaste källan av PFAS i Kungsängsverket. Det visades tydligt att PFAS i ett kommunalt avloppsvatten kan ha sitt ursprung såväl i både industriella produkter och processer som produkter från hushåll, som t.ex. dagligvaruprodukter. Den nya kunskapen som genererats i detta projekt kommer att hjälpa Uppsala Vatten att skydda dricksvattentäkter och den mottagande akvatiska miljön för PFAS förorening.

Småskaliga processindustrier är små industrier som genom ett småskaligt, hantverksmässigt eller lokalt förhållningssätt förädlar råvaror genom olika automatiserade processer. Vid förädlingen uppkommer stora mängder processavloppsvatten med stor organisk belastning som måste tas om hand på ett hållbart, resurseffektivt och miljömässigt sätt för att inte skada människa eller miljö. I denna studie undersöktes kvaliteten på processavloppsvatten från småskaliga slakterier, mejerier och bryggerier, samt hur hanteringen av processavloppsvattnet från dessa processindustrier ser ut i Sverige idag. Ytterligare utreddes hur reningstekniker för små avlopp kan användas för rening av processavloppsvatten från småskalig processindustri samt hur marknaden för användande av tekniker för små avlopp för rening av processavloppsvatten ser ut. Studien använde ett flertal metoder, litteraturstudie av småskaliga processindustrier och små avlopp, intervjuer och enkätundersökning av småskaliga slakterier, mejerier och bryggerier, samt intervjuer med tillverkare för tekniker för små avlopp. Resultatet visade att kvaliteten på processavloppsvattnet inte kunde redovisas för majoriteten av processindustrierna från intervjuer och enkätundersökning eftersom kvalitetsanalyser inte alltid verkar ske på processavloppsvattnet, varken före eller efter rening. Litteraturen beskrev vidare att prioriterade parametrar att rena för slakterier, mejerier och bryggerier främst är organiska ämnen (mätt som BOD eller COD), suspenderade ämnen, kväve, fosfor, samt pH. Dessa parametrar varierar mellan de olika typerna av processindustrierna och inom samma typ av processindustri. Variationerna anses utgöra en utmaning att hitta passande reningstekniker som fungerar i alla sammanhang. Angående vilka reningstekniker och avloppslösningar som används av småskaliga processindustrier visade resultatet att en stor andel av processindustrierna har intern rening, och knappt en tredjedel har anslutning till kommunalt avloppsnät. Processindustrier med intern rening vars processavloppsvatten dimensionerades till mindre än 100 personekvivalenter använder till övervägande del tekniker för rening av små avlopp, men andra avloppslösningar såsom gödselbrunn, reningsverk och biogasanläggning förekom även för större avloppsdimensioner. Reningstekniker för små avlopp för rening av processavloppsvatten, samt anpassade tekniker för processavloppsvatten, erbjuds till viss grad på dagens marknad men det finns fortfarande utmaningar för att kunna tillhandahålla lösningar för fler typer av processindustrier. Möjlighet att utjämna avloppsflöden och lösningar med större belastningskapacitet är fortfarande något som behöver utvecklas vidare. / Small-scale process industries are small, sometimes locally or artisanal, industries that produces their product through processing raw materials by using automated processes. Large volumes of wastewater effluent are produced by doing this, and this wastewater is characterized by high organic load and nutrients which must be treated in a sustainable way to not be harmful to humans nor the environment. This study evaluated industrial wastewater treatment from small-scale slaughterhouses, dairies and breweries, including wastewater characteristics of these types of process industries in Sweden today. The study also included an evaluation of decentralized wastewater treatment systems for small-scale industrial wastewater treatment and what the Swedish market can provide regarding small-scale industrial wastewater treatments. Different methods were used to reach this goal; a literature study regarding wastewater characteristics and treatment of industrial wastewater and decentralized wastewater treatment systems, interviews, and surveys of Swedish small-scale process industries, and finally interviews with manufacturers of decentralized wastewater treatment systems. The result showed that wastewater characteristics was not accessible from most of the Swedish small-scale process industries. They mostly do not analyze their wastewater neither before nor after wastewater treatment. Furthermore, it was described that highpriority wastewater characteristics for treatment according to the literature was BOD, COD, suspended solids, nitrogen, phosphorus, and pH. Variations of these characteristics is common both between different types of process industries and in the same type of industry. These variations are challenging in regard to finding suitable wastewater treatment techniques that is adequate in every situation. Wastewater treatment systems used today are mostly local at the site, it is around a third that have connection to municipal wastewater facilities. The most common local wastewater treatment for small process industries (less than 100 population equivalents) is decentralized wastewater treatment systems according to the interviews and surveys. Other wastewater treatments such as dung pits, wastewater treatment plants and biogas plants were also used for larger process industries. Decentralized wastewater treatment systems for industrial wastewater treatment and adapted small-scale industrial wastewater treatments can be found to some extent on the Swedish market today, but there are still some challenges to provide small-scale industrial wastewater treatment for every type of process industry. Solutions to level out intense wastewater flows and capacity to receive high effluent loads need to be further developed.

Thesis (MScEng (Chemical Engineering))--University of Stellenbosch, 2001. / 304 leaves single sided printed,preliminary pages i-xxii and numberd pages 1-282. Includes bibliography,list of figures and tables, used a Bizhub 250 Scanner to pdf format (OCR) 57pages contain figures in color.Digitized at 300 dpi 24-bit Color to pdf format (OCR),used a Hp Scanjet 8250 / ENGLISH ABSTRACT: Ecosystems and natural water sources are constantly under threat from pollutants and all efforts should be made to minimise polluting factors. In the last decade growing concern has been expressed with regard to the environmental threat posed by wastewater produced by wineries and distilleries. Research into winery wastewater commenced in the early nineties mainly in Australia and France. These investigations characterised winery wastewater, indicating a large diversity in quality and quantity between wastewaters emanating from wineries. Owed to changes in South African legislation, in conjunction with an augmented environmental awareness, the need for an environmental assessment of wineries became apparent. In South Africa, research of this nature had not yet been conducted. Previous research on winery wastewater treatment employed mostly biological technologies, with success but also shortfalls. In South Africa the majority of wineries are located in the Western Cape Province, several within the same water catchment area. Wineries may produce approximately 1 to 10 litres of wastewater per litre of wine produced, which are turbid and acidic and typically contain high levels of organic compounds (thus oxygen deficient), and suspended material. Usually these wastewaters are irrigated onto land, in close proximity to natural water resources. The pollution of water tables and down-stream water sources may occur. The quantification, qualification and treatment of this type of wastewater are addressed in this study. Winery wastewater produced from the predominantly red wine producing Rupert and Rothschild Vignerons, served as case study for a two-year wastewater audit strategy. The most common analyses performed on winery wastewater include the Chemical Oxygen Demand (COD), suspended solids (SS), pH and turbidity. A thorough analysis in the form of a comprehensive audit was performed on the water and vinification processes. This allowed for an accurate determination of contamination sources and properties. The audit entailed a designed sampling protocol, the format of which was tailored as an initial environmental assessment for the development of an Environmental Management System (EMS) unique to Rupert and Rothschild Vignerons. The EMS includes projected future objectives for wastewater quality (COD, SS, pH, turbidity), as well as an environmental policy. In order to reach the proposed quality objectives, a suitable wastewater treatment system must be installed. The efficiency of the treatment system present at Rupert and Rothschild Vignerons was evaluated and piloted the investigation of physico-chemical treatment technologies. Research into the applicability of induced sedimentation (coagulation) and chemical oxidation (ozone) was the first of its kind for winery wastewater as substrate, and provided an interesting dimension in the sense of pragmatic and economic feasibility. Dissolved and suspended particles present in winery wastewater do not settle by gravity alone, thus requiring sedimentation agents (coagulants). Benchscale experiments were conducted employing four types of pre-polymerised metal salt coagulants (polyaluminium chloride). Successful sedimentation of turbidity inducing compounds (up to 98 %) and suspended solid fractions (up to 92%) was achieved. These coagulants are highly suitable for the treatment of winery wastewater since the investigation showed that they are effective over a broad pH and dosage range. In addition, rapid sedimentation rates were observed, favouring thickener design economy. Ozone is a potent oxidising agent, and has been reported to increase the biodegradability of dissolved organic compounds and result in the decolouring of wastewaters. Ozonation is highly pH dependent, with hydroxyl radical activity dominating at alkaline pH. In the majority of gas-liquid contacting systems, the kinetics of the heterogeneous reaction is not limited by the chemical reaction rate, but by the transport of ozone to the liquid phase. To compensate, the ozone concentration in the gas phase is increased. Coupled to the primary investigation on the applicability of ozone treatment for winery wastewater, thus emerged a secondary investigation into an enhanced mass transfer system, realised by the use of impinging stream technology. The ozone transfer in a conventional bubble-column was compared to that of an impinging-stream jet-reactor. The latter significantly improved the ozone transfer to the winery wastewater, resulting in the rate-limiting step being the chemical reaction rate. Ozonation resulted in the increased biodegradability of the winery wastewater, and complete colour and odour elimination. Concerning jet-reactors, the principal importance lies in the substantial reduction in the initial ozone concentration requirement, thereby rendering the process more economically feasible. Following the investigation of the wastewater dynamics, the determination of eco-toxicology during irrigation should be conducted in future. When considering induced sedimentation, further studies should be directed towards ascertaining the most economic yet efficient dosage of the coagulant. Similarly, a study concerning the economic viability of ozone efficiency should be realised in terms of the energy requirements for both ozone generation and the operation of jet-reactors. Although the jet reactor poses a benefit for enhanced mass transfer, the essential criterion concerning residence time in the reactor must be addressed for positive results. Since no single solution exists for the treatment of winery wastewaters, the application of the considered technology must be carefully selected and incorporated in a treatment design; the two foremost criteria for selection being efficiency and economy. / AFRIKAANSE OPSOMMING: Ekologiese stelsels en natuurlike waterbronne word gedurig bedreig deur besoedeling, dus moet ten aile tye gepoog word om besoedeling te minimiseer of te voorkom. Gedurende die laaste dekade is al hoe meer kommer uitgespreek oor die besoedeling van afloop water afkomstig van wyn en spiritualiee-vervaardiging. Navorsing aangaande wynafloopwater het ontstaan in die vroee negentigs, hoofsaaklik in Australie en Frankryk. Hierdie navorsing het gelei tot die karakterisering van wynafloopwater, en die uiteenlopendheid van hierdie water aangaande die kwaliteit en kwantiteit tussen kelders, is aangetoon. As gevolg van veranderinge in die SuidAfrikaanse wetgewing, asook 'n groeiende bewuswording van omgewingsake, het die noodsaaklikheid van omgewings impak-studies vir wynkelders na vore getree. Tot op hede is navorsing van hierdie aard nog nie in Suid Afrika gedoen nie. Vorige navorsing op die behandeling van wynafloopwater het meestal biologiese tegnologiee behels, met 'n mate van sukses maar ook met tekortkominge. Die meederheid wynkelders in Suid Afrika is in die Wes-Kaap gelee, baie binne dieselfde opvanggebied. Wynkelders kan tussen 1 tot 10 liter afloop water produseer per liter wyn geproduseer. Hierdie afloop het tipies 'n hoe konsentrasie organiese stowwe (is dus arm aan suurstof), is troebel en suur, en bevat gesuspendeerde materiaal. Gewoonlik word die wynafloop water besproei in die nabyheid van natuurlike waterbronne. Die besoedeling van watertafels en waterbronne kan dus plaasvind. Die kwantifisering, kwalifisering en behandeling van wynafloopwater word ondersoek in hierdie tesis. Die wynafloopwater van die hoofsaaklik rooiwyn produserende Rupert en Rothschild Vignerons, het gedien as proefstudie tydens 'n twee-jaar wynafloopwateroudit. 'n Deeglike analise in die formaat van 'n veelomvattende oudit is uitgevoer op die wynmaakproses en die waterafvoerstrome. 'n Akkurate bepaling van die oorsprong van waterkontaminasie, asook die eienskappe daarvan is bewerkstellig. Die oudit behels 'n spesifiek ontwerpte monsternemingprotokol, waarvan die formaat geformuleer is om te dien as 'n beginpunt vir die ontwikkeling van 'n Omgewingsbestuurstelsel (08S), uniek vir Rupert en Rothschild Vignerons. Hierdie 08S sluit toekomstige doelstellings vir die kwaliteit (chemiese suurstofbehoefte, gesuspendeerde vaste stowwe, pH, turbiditeit) van wynafloopwater in, asook 'n omgewingsbeleid. Die installering van 'n waterbehandelingsisteem moet geskied om te voldoen aan hierdie voorgestelde doelstellings. Die effektiwiteit van die huidige behandeling sisteem teenwoordig by Rupert en Rothschild Vignerons is geevalueer en het gelei tot navorsing oor fisieschemiese behandelingstegnologiee. Navorsing aangaande die toepassing van geinduseerde sedimentasie (koagulasie) en chemiese oksidasie (osoon), is vir die eerste keer toegepas op wynafloopwater, en het interessante gevolge in 'n pragmatiese en ekonomiese sin. Opgelosde en gesuspendeerde partikels teenwoordig in wynafloopwater sak nie onder normale gravitasie uit nie, en dus word die toediening van sedimentasie-induserende middels benodig. Eksperimente is in die laboratorium uitgevoer met vier verskillende gepolimeriseerde metaalsoutkoagulante (poli-aluminiumchloriedes). Dit het gelei tot die effektiewe sedimentering van stowwe wat troebelheid (turbiditeit) veroorsaak (tot 98 %) en ook gesuspendeerde stowwe (tot 92 %). Dit is gevind dat hierdie tipe koagulante hoogs geskik is vir die behandeling van wynafloop water, aangesien hulle effektief is by 'n wye pH- en doseringsreeks. Die uitsaktempo is vinnig, wat dus die ontwerp van 'n uitsaktenk (verdikker) ekonomies maak. Osoon is 'n sterk oksideermiddel, terwyl talle verslae aandui dat dit die biologiese ontbinding van opgelosde stowwe verhoog en die ontkleuring van afloopwaters tot. gevolg het. Osonering is pH afhanklik; by alkaliese pH oorheers die werking van hidroksielradikale. In die meerderheid gasvloeistofkontaksisteme word die kinetika van die heterogene chemiese reaksie nie beperk deur die intrinsieke reaksietempo nie, maar deur die vervoer van osoon na die vloeistoffase. Om te kompenseer hiervoor, word die osoon konsentrasie in die gasfase verhoog. Gekoppel aan die primere ondersoek aangaande die toepasbaarheid van osoonbehandeling op wynafloopwater, het 'n tweede ondersoek onstaan aangaande verhoogde massa-oordragssisteme deur die gebruik van hoeintensiteit spuitreaktore. Die osoonoordrag in konvensionele borrelkolomme is vergelyk met die van 'n hoe intensiteit spuitreaktor. Laasgenoemde het die osoonoordrag na die wynafloopwater aansienlik verhoog, met die gevolg dat die chemiese reaksie die beperking op die reaksie tempo geplaas het. Osonering het die biodegradasie van die wynafloop water verhoog, asook die kleur en reuk verwyder. By die spuit-reaktor Ie die belangrikheid daarin by die aansienlike veriaging in die aanvanklike behoefte aan osoonkonsentrasie, derhalwe is hierdie oordragsisteem meer ekonomies. Na afloop van die ondersoek op die dinamika van wynafloopwater, moet die ekotoksisiteit gedurende besproeiing bepaal word vir toekomstige doeleindes. Indien ge"induseerde sedimentasie verlang word, kan verdere studie gedoen word om die mees ekonomiese dosis van die koagulant te bepaal. Ooreenstemmend, moet die ekonomiese lewensvatbaarheid van die osoon effektiwiteit bepaal word ten opsigte van die energiebehoefte van beide die osoongenerasie en die werking van die hoe-intensiteit spuitreaktor. Alhoewel die spuitreaktor verhoogde massa-oordrag bewerkstellig, moet die effek van die residensietyd in die reaktor inag geneem word word ten einde positiewe resultate te verkry. Geen enkele oplossing bestaan vir die behandeling van wynafloop water nie, derhalwe moet die toepassing van die beoogde sisteem versigtig gekies word en ingesluit word in die ontwerp van 'n behandelingsisteem; die twee vernaamste maatstawwe is ondermeer effektiwiteit en ekonomiese aspekte.

This thesis examines the impact of urban water infrastructure on the Ottawa River through an exploration of the City of Ottawa's historical development from the early modern period to the present. The primary aim is to explain how the Ottawa River came to be removed or ignored from the City of Ottawa's urban development strategy. The thesis focuses on the periods of 1910-1920 (early modernity) and 1999-2012 (present). The theories applied are risk, risk management, normal accident theory and the politics of infrastructure. The data and information for this thesis were primarily retrieved from the City of Ottawa website as well as from the archives of the City of Ottawa. The thesis identifies several factors explaining why the Ottawa River has been mistreated over time, as well as the challenges involved in reforming present-day practices and infrastructure. Several recommendations to fix the situation are advanced.

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology| / The co-existence of organic acids and toxic heavy metals in natural water creates harmful effects on human, plants and animals. Therefore, it is necessary to treat organic acids and toxic heavy metal contaminated wastewater prior to its discharge to the environment. The aim of this study was to apply co-treatment of industrial wastewater containing citric acid and toxic heavy metals in single and binary systems using photocatalysis process. The hydrothermal method was used to synthesise dandelion-like TiO2 structures. Modifications of the dandelion-like TiO2 by deposition of gold nanoparticles and immobilisation on calcium alginate were done using deposition precipitation and one-step encapsulation methods, respectively. Dandelion-like TiO2 and dandelion-like TiO2 immobilised on calcium alginate (Alg/TiO2) were used as photocatalysts for Cr(VI), Hg(II) and citric acid removal from water. The results showed that the production of dandelion-like TiO2 structures strongly depends on the reaction time and synthesis temperature as key process parameters. The characterisation of the dandelion-like TiO2 by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and Brunauer-Emmett-Teller (BET) revealed the crystal structure, morphology, chemical composition and surface area. It was found that the efficiency of photocatalytic process depends on the type of pollutants, initial pH of the solution, photocatalyst dosage, contact time, substrate initial concentration, UV wavelength and light intensity. The reduction efficiency of Cr(VI) ion and citric acid increased with decreasing the initial pH values and initial concentration. On the other hand, Hg(II) reduction efficiency increased with increasing the initial pH values and initial concentration. In a binary system, the reduction of Cr(VI) and Hg(II) was found to be faster than in the single and ternary systems. The relationship of the chemical reaction rate of Cr(VI), Hg(II) and citric acid were expressed by the pseudo-first-order kinetic equation. Addition of ferric ions to Cr(VI)-citric acid complex and Hg(II)-citric acid complex enhanced the reduction of Cr(VI) and Hg(II), a complete reduction was accomplished within 30 and 60 minutes (min) of irradiation time, respectively. The reduction efficiency of both Cr(VI) and Hg(II) in the presence of citric acid in a solution was still significant after four times of Alg/TiO2 reuse. These results indicated that the UV/TiO2 photocatalysis process can be considered as a suitable method to reach a complete reduction of Cr(VI) and Hg(II) in the presence of citric acid in a solution.

En France, 13 millions de personnes sont concernées par l’assainissement non collectif (ANC). Un système d’ANC est composé d’un prétraitement, en général une fosse toutes eaux, suivi d’un système de traitement. Les récentes évolutions réglementaires ouvrent un éventail de possibilités quant aux systèmes de traitement possibles pour traiter les eaux usées. L’objectif de ce travail de thèse est de développer un système de traitement des eaux usées à partir de biomasse végétale issue de déchets de l’agriculture. Un suivi analytique de six habitations individuelles a permis l’étude des caractéristiques des eaux usées avant et après leur entrée dans le système de prétraitement. Ces eaux sont caractérisées par une grande variabilité d’une famille à une autre ainsi qu’au sein d’une même habitation. La charge organique par habitant à traiter est en moyenne de 60 gDBO5.j-1 pour un volume d’eau rejeté de 90 L.j-1, soit des effluents deux fois plus concentrés que ce qu’indique la réglementation. Le dimensionnement et le suivi d’un pilote à l’échelle laboratoire ont permis d’évaluer la potentialité de plusieurs milieux végétaux pour le traitement des eaux usées prétraitées. Ils sont comparés à un milieu de référence ayant une efficacité prouvée en traitement des eaux. L’étude des performances épuratoires, pour deux charges volumiques différentes, des différents milieux a été réalisée sur quarante semaines. Cette étude a permis l’élaboration et la mise en place d’un pilote in situ à l’échelle de la maison individuelle. La démarche de l’analyse de cycle de vie a été appliquée au pilote in situ dans le but d’optimiser le procédé mis en place. De plus, l’ACV a permis d’effectuer une comparaison avec différents procédés existants. / In France, 13 million people are concerned by on-site wastewater treatment (OSWWT). An OSWWT system consists of pretreatment, usually a septic tank, followed by a treatment system. Recent regulatory developments open up a range of possibilities as to possible treatment systems for wastewater treatment. The objective of this thesis is to develop a system of wastewater treatment based on plant biomass from waste of agriculture. Analytical monitoring of six individual houses allowed the study of the characteristics of the wastewater before and after their entry into the pretreatment system. Waters are characterized by a wide variability from one family to another and from the same house. The organic load per person is treating an average of 60 gDBO5.j-1 for a volume of water discharged 90 L.j-1, that to say effluent two times more concentrated than indicated by the regulations. The design and monitoring of a pilot scale laboratory were used to evaluate the potential of several plant biomass for the treatment of pretreated wastewater. They are compared to a reference medium with proven effectiveness in water treatment. The study of treatment performance for two different volume loads of different backgrounds was performed during forty weeks. This study resulted in the development and implementation of a pilot in situ for single house. The approach of life cycle analysis has been applied to in situ pilot in order to optimize the process in place. In addition, LCA has to make a comparison with different existing OSWWT.

Ce travail a permis d'acquérir de nouvelles connaissances sur la micropollution issue de l'activité domestique. Un état des lieux a été réalisé sur la présence de certains micropolluants dans les eaux usées (dans les phases liquide et solide) de deux zones urbaines, résidentielle et mixte (habitats, hôpital, administrations), et dans deux stations d'épuration (STEP) biologiques. Les micropolluants étudiés ont été choisis selon leurs usages et en fonction de leurs propriétés physico-chimiques afin de mieux appréhender leur répartition entre les phases liquides et solides. Dans un premier temps, les méthodes d'extraction et d'analyse des micropolluants dans les matrices liquides (eau usée et eau traitée) et solides (matières en suspension et boue) ont été développées et validées. Les prélèvements d'eaux usées dans les égouts des deux zones urbaines ont mis en évidence différents usages de certains composés en fonction de la zone urbaine et de la saison (été ou hiver). Les mesures des concentrations en micropolluants en entrée et en sortie de STEP dans les eaux et les boues ont permis d'évaluer leurs rendements d'élimination et ont révélé une différence d'efficacité entre les deux STEP biologiques. Une étude statistique a montré qu'il existe des corrélations entre les concentrations en micropolluants et en macropolluants (DCO, ammonium, et turbidité) en entrée et en sortie de chacune des STEP étudiées. L'effet des micropolluants sur l'activité bactérienne a été examiné en conditions de laboratoire par des tests de toxicité sur Escherichia coli et par des expériences sur la biomasse de STEP en réacteur batch / This work allowed to acquire new knowledge on micropollution issued from household activities. The occurrence of some micropollutants in urban wastewater (liquid and solid phases) of two urban areas, residential and mixed (houses, hospital, administrations), and in two biological wastewater treatment plants (WWTPs) was assessed. The studied micropollutants were chosen according to use and as function of their physical and chemical properties in order to consider their partitioning between liquid and solid phases. Firstly, the methods for the extraction and the analysis of micropollutants in liquid and solid matrices (wastewater and treated water, suspended matter and sludge) were developed and validated. Wastewater sampling in the sewers of the two urban catchments showed some differences of the use of certain compounds according to the catchment and to the season (summer or winter). Measurements of micropollutant concentrations at the inlet and outlet of the plants, on water and sludge, allowed to assess their removal yields and revealed a difference of efficiency of the two biological WWTPs. A statistical treatment showed that there are some correlations between concentrations of micro and macropollutants (COD, ammonium and turbidity) at the inlet and at the outlet of each studied WWTPs. The effect of the target micropollutants on bacterial activity was evaluated under laboratory conditions, by toxicity tests on Escherichia coli, and by experiments on biological sludge in batch reactors

Une méthode miniaturisée de fractionnement de la Demande Chimique en Oxygène (DCO) dans les eaux usées a été développée pour vérifier une possible variabilité à court terme de ce fractionnement et son influence sur le comportement des installations d’épuration par boues activées. Des tests de biodégradabilité, en réacteur fermé, ont été effectués avec des échantillons moyens horaires de temps sec (24h) provenant de deux stations d’épuration urbaines. Les analyses réalisées ont concerné la DCO totale et soluble, la Demande Biologique en Oxygène, les matières sèches et en suspension, l’ammonium et ont été complétées par des analyses spectrales (UV-visible et fluorescence). Globalement, en accord avec les données de la littérature, les fractions biodégradables sont les plus importantes en terme de concentration. Une variabilité journalière du fractionnement a été observée, sans qu’il soit possible de dégager des tendances particulières indiquant la prééminence de telle ou telle fraction. L’effet de la variabilité du fractionnement a été testé en boucle ouverte en utilisant un schéma classique d’épuration du carbone et de l’azote dans un simulateur de référence, le Benchmark Simulation Model 1. Les simulations ont permis de vérifier l’importance de la variabilité du fractionnement de la DCO sur une station d’épuration. Les concentrations en DCO dans l’effluent sont affectées par le rapport entre la fraction biodégradable et inerte, mais restent dans une limite acceptable par rapport aux normes de rejet. La situation est différente et plus délicate pour les rejets en matières azotées car ils sont proches des limites fixées par la réglementation / A miniaturized method has been developed for the fractionation of Chemical Oxygen Demand (COD) in wastewater in order to assess its variability and its effects on the behaviour of wastewater treatment plants by activated sludge. Biodegradability tests have been performed in batch reactor on daily composite samples grabbed by dry weather with a 1h sampling interval. The method has been applied on samples from two urban wastewater treatment plants. The samples were analysed for total and soluble COD, Biological Oxygen Demand, turbidity, total suspended solids and N-NH3. UV-visible and fluorescence spectra have also been collected. It has been observed, as in literature, that the biodegradable fractions are the most significant ones in terms of concentration. A variability of the fractionation during the day has been observed, although it was not possible to determine definite tendencies for particular fractions. In order to evaluate the effect of the variability of the fractionation, the Benchmark Simulation Model n°1 has been used. The sensibility analysis has been performed in open loop. The simulations allowed verifying the impact of the variability of the fractionation on a treatment plant based on a classical setup for the treatment of carbon and nitrogen. The COD concentrations of the plant effluent are affected by the ratio between the biodegradable fraction and the non-biodegradable one, although staying in an acceptable limit according to the discharge limits. The same is not true for the nitrogen, which are close to these limits

Neste trabalho, a partir da aplicação da teoria de controle ótimo, são estabelecidos sistemas de controle aplicáveis a três importantes sistemas aeróbios de tratamento de esgotos - filtros biológicos, processos de lodos ativados e os processos combinados formados a partir da combinação dos filtros biológicos e lodos ativados. Para a definição dos sistemas de controle são necessários modelos dinâmicos que descrevam o comportamento dos diferentes sistemas de tratamento. Da literatura são obtidos os modelos dinâmicos destinados à descrição do comportamento do processo de lodos ativados; para o filtro biológico, é proposto um modelo combinando à equação de balanço do reator e o modelo de ordem variável, este último destinado ao cálculo do fluxo de substrato para o interior de biofilmes profundos. Os resultados demonstram que, independentemente do sistema de tratamento considerado, os sistemas de controle reduzem substancialmente os tempos de acomodação e os desvios apresentados pelas variáveis de estado em relação as suas condições de equilíbrio. Por fim, função da inviabilidade de monitoramento de todas as variáveis de estado utilizadas para caracterizar os sistemas de tratamento, são propostos, a partir de modelos simplificados, controladores que incorporam a observação de estados. Também neste caso, os controladores estabelecidos permitem melhorar significativamente o desempenho dos sistemas de tratamento de esgotos analisados. / This paper constructs automatic control systems by means of optimal control theory for three different combinations of wastewater treatment units, namely, trickling filter, activated sludge process and a combined process. The dynamic model for the activated sludge process available in literature and a model proposed for the trickling filter were used in the construction of control systems. It is shown that the controls obtained in this study substantially reduce the durations necessary for the reestablishment of the equilibrium conditions in terms of state variables and the attenuation of oscillations around these conditions. Controls including observers for the state variables were devised on the basis of simplified models for the process in order to deal with the difficulties involved in monitoring all the state variables. These control systems were also found to be quite effective in improving the performance of the wastewater treatment plants considered in this paper.

Apesar dos avanços nos índices de coleta e tratamento de esgotos no Estado de São Paulo, ainda existem incertezas sobre a efetividade dos sistemas de tratamento existentes, uma vez que são escassas as informações sobre o desempenho das ETEs em operação no país. Por meio da aquisição e análise de dados de desempenho do sistema, é possível a avaliação do cumprimento da legislação ambiental e a melhoria das condições operacionais, reduzindo, efetivamente, o impacto do lançamento sobre os recursos hídricos. Nesse sentido, o presente trabalho teve como objetivo avaliar estatisticamente o desempenho de lagoas de estabilização - tecnologia de tratamento mais utilizada no Estado de São Paulo - localizadas na UGRHI 12 - Baixo Pardo/Grande, todas com vazão de projeto inferior a 300 L/s, utilizando dados de automonitoramento fornecidos pelos prestadores de serviço. A avaliação compreendeu um período de 10 anos (2005 a 2014) e abrangeu desde os projetos das lagoas até a caracterização dos dados afluentes e efluentes das ETEs, incluindo também o impacto do lançamento dos esgotos tratados nos corpos receptores e a qualidade dos corpos d\'água em escala de bacia hidrográfica, utilizando os dados da rede de monitoramento da CETESB na UGRHI 12. O desempenho das ETEs foi avaliado quanto aos parâmetros DBO, DQO, CT, E. coli, SS, N-amoniacal e P-total, considerando tanto as faixas típicas apontadas na literatura, como o atendimento aos padrões de lançamento e qualidade. Os dados disponibilizados foram bastante heterogêneos, apresentando, em sua maioria, periodicidades de amostragem variáveis e interrupções no monitoramento, o que impediu, em alguns casos, a realização de uma análise mais consistente. As concentrações afluentes de matéria orgânica foram mais elevadas do que os valores usuais expressos na literatura, sendo a causa mais provável o baixo consumo de água aliado ao tipo de amostragem praticado (amostragem simples). De maneira geral, o desempenho das lagoas, considerando as eficiências médias de remoção de DBO e DQO, ficou dentro do esperado, o que não foi suficiente, contudo, para garantir percentuais elevados de conformidade com a legislação do estado de São Paulo, os quais resultaram abaixo de 80% na maioria das ETEs. Quanto às concentrações nos esgotos tratados, o desempenho ficou aquém do esperado, o que implicou no lançamento de efluentes com concentrações elevadas de matéria orgânica, embora de acordo com os padrões de lançamento pelo critério da eficiência de remoção. A avaliação do corpo receptor mostrou que, mesmo se tratando de vazões relativamente baixas, tais lançamentos foram capazes de impactar os cursos d\'água, notadamente aqueles com baixas razões de diluição. Finalmente, em escala de bacia hidrográfica, verificou-se que, nos corpos d\'água da UGRHI 12, ainda permanecem percentuais elevados de desconformidade para P-total e E. coli, contribuindo para esse cenário tanto as fontes de poluição pontuais como as difusas. / Despite advances in wastewater collection and treatment indicators in São Paulo state, there are still uncertainties about the effectiveness of existing treatment systems, since they is little information on the performance of WTPs operating in the country. Throughout the acquisition and analysis of system performance data, it is possible to evaluate the compliance with environmental legislation and improve operating conditions, effectively reducing the impact of the discharge on water resources. In this sense, the present study aimed to evaluate statistically the performance of stabilization ponds - wastewater treatment technology most widely used in São Paulo state - located in UGRHI 12 - Baixo Pardo/Grande, all of them with design flow rates below 300 L/s, using self-monitoring data given by the service providers. The evaluation comprised a period of 10 years (2005-2014), including from the projects of the ponds to the characterization of WTPs influent and effluent data, also incorporating the impact of treated wastewater release in receiving bodies and the quality of water bodies in watershed scale, using the data from CETESB\'s monitoring network in UGRHI 12. The performance of the WTPs was evaluated for BOD, COD, total coliforms, E. coli, suspended solids, ammonia and total phosphorus, considering the typical ranges mentioned in the literature and compliance with discharge and water quality standards. The provided data were quite heterogeneous, most of them presenting variable sampling periodicities and interruptions in monitoring, sometimes hindering a more consistent analysis. The influent\'s concentrations of organic matter were higher than the usual values expressed in the literature, which was most likely caused by low water consumption combined with the type of sampling practiced (single sampling). In general, the ponds\' performance, considering the average BOD and COD removal efficiencies, was as expected, however, such values weren\'t enough to ensure high percentage of compliance with São Paulo\'s environmental legislation, since the percentages were below 80% in most WTPs. Regarding the concentrations in treated wastewater, the performance was less than expected, which resulted in the discharge of effluents with high concentrations of organic matter, even though they were in compliance with discharge standards by the removal efficiency criterion. The evaluation of the receiving stream showed that, even consisting of relatively low flow rates discharges, such releases were able to impact the water bodies, especially those with low dilution ratio. Finally, in watershed scale, it was found that, in UGRHI 12 water bodies, there are still high percentages of non-conformity for total phosphorus and E. coli, contributing to this scenario both point and non-point sources of pollution.