学位授与年月日: 2007-07-23 ; 学位の種類: 新制・課程博士 ; 学位記番号: 工博第2837号 / Perfluorochemicals (PFCs) were produced by industries and consumed “safely” as surfactants, repellents, additives, fire-fighting foams, polymer emulsifiers and insecticides for almost fifty years. However they are now considered as persistent, bioaccumulated and toxic (PBT) chemicals, and ubiquitously distributed in waster, air, human body and biota. Although some efforts were contributed to reduce PFCs in environment, such as development of alternatives and recycling processes, huge amount of persisted PFCs have already been discharged in environment and accumulated in biota including humans. In some industrialized areas, such as Yodo river basin in Japan, water environment and human blood were polluted by some PFCs, and thus reduction and control of PFCs were urgently required for the purpose of environmental safety and human health in these areas. Unfortunately, some studies implied that current water and wastewater treatment processes seemed ineffective to remove PFCs in trace levels. Therefore, this study will try to develop some proper technologies to treat trace level of PFCs in wastewater. In order to achieve this main objective, several works have been accomplished as follows. 　Current available literature has been reviewed to obtain a solid background for this study. Basic information of PFCs was summarized in physiochemical properties, PBT properties, productions and applications, regulations and etc.. Analytical methods for PFCs, especially of LC-ESI-MS/MS, were reviewed including pretreatment processes in diverse matrices, which derived objectives of chapter III. Distributions and behavior of PFCs were briefly discussed in water environments, biota sphere and human bloods. Available control strategies were shown in detail about alternatives, industrial recycling processes, and newly developed treatment processes. Current wastewater treatment processes showed inefficient removal for some PFCs, deriving objectives of chapter IV on the PFC behavior in treatment process. Newly developed treatment technologies seemed able to decompose PFCs completely but unsuitable for application in WWTP. Therefore, granular activated carbon (GAC) adsorption and ultra violet (UV) photolysis were developed in chapter V and VI as removal and degradation processes respectively. 　Fifteen kinds of PFCs were included in this study, consisting of twelve kinds of perfluorocarboxylic acids (PFCAs) with 4~18 carbons and three kinds of perfluoroalkyl sulfonates (PFASs) with 4~8 carbons. An integral procedure was developed in chapter III to pretreat wastewater samples. LC-ESI-MS/MS was applied to quantify all PFCs in trace level. Pretreatment methods were optimized between C18 and WAX-SPE processes for aqueous samples, and between IPE, AD-WAX and ASE-WAX processes for particulate samples. Standard spiking experiments were regularly conducted for each wastewater sample to calculate recovery rate and control analytical quality. As the result, WAX-SPE showed better performance on samples with very high organics concentrations, and C18-SPE performed better for long-chained PFCs. ASE-WAX was proposed as the optimum method to pretreat particulate samples because of the simple and time saving operations. 9H-PFNA was used as internal standard to estimate matrix effect in wastewater. 　Behavior of PFCs in a municipal WWTP has been studied in chapter IV by periodical surveys for six times in half a year. All PFCs used in this study were detected in WWTP influent and effluent. According to their carbon chain lengths, all PFCs can be classified into “Medium”, “Long” and “Short” patterns to simplify behavior analysis. PFCs in same pattern showed similar properties and behavior in wastewater treatment facilities. Very high concentrations of PFCs existed in WWTP influent, indicating some point sources of industrial discharge in this area. “Medium” PFCs, such as PFOA(8), PFNA(9) and PFOS(8), were primary contaminants in the WWTP and poorly removed by overall process. Performances of individual facilities were estimated for removal of each PFC. Primary clarification and secondary clarification were helpful to remove all PFCs in both aqueous phase and particulate phase. “Medium” PFCs in aqueous phase were increased after activated sludge process, but other PFCs can be effectively removed. Ozone seemed ineffective to decompose PFCs because of the strong stability of PFC molecules. Sand filtration and biological activated carbon (BAC) filtration in this WWTP can not remove PFCs effectively too, which required further studies. Performances of combined processes were estimated by integrating individual facilities along the wastewater flow. Activated sludge process coupled with clarifiers showed satisfied removal of most PFCs in the investigated WWTP except “Medium” PFCs. 　Adsorption characteristics of PFCs onto GAC have been studied by batch experiments in chapter V. Freundlich equation and homogenous surface diffusion model (HSDM) were applied to interpret experimental data. Isothermal and kinetics experiments implied that PFC adsorption on GAC was directly related with their carbon chain lengths. By ascendant carbon chain length, adsorption capacity for specific PFC was increased, and diffusion coefficient (Ds) was decreased. Ds of GAC adsorption was also decreased gradually in smaller GAC diameters. Coexisted natural organic matters (NOMs) reduced adsorption capacities by mechanism of competition and carbon fouling. Carbon fouling was found reducing adsorption capacity much more intensively than competition by organics. Acidic bulk solution was slightly helpful for adsorption of PFCs. However adsorption velocity or kinetics was not affected by NOM and pH significantly. GAC from Wako Company showed the best performance among four kinds of GACs, and Filtra 400 from Calgon Company was considered more suitable to removal all PFCs among the commercial GACs. Preliminary RSSCT and SBA results implied that background organics broke through fixed GAC bed much earlier than trace level of PFCs. Medium-chained PFCs can be effectively removed by fixed bed filtration without concerning biological processes. 　Direct photolysis process has been developed in chapter VI to decompose PFCAs in river water. Irradiation at UV254 nm and UV254+185 nm can both degrade PFCAs. Stepwise decomposition mechanism of PFCAs was confirmed by mass spectra analysis, and consecutive kinetics was proposed to simulate experimental data. PFASs can also be degraded by UV254+185 photolysis, although the products have not been identified yet. Coexisted NOMs reduced performance of UV photolysis for PFCAs by competition for UV photons. Sample volume or irradiation intensity showed significant influence on degradation of PFCAs. Local river water polluted by PFOA can be cleaned up by UV254+185 photolysis effectively. Ozone-related processes were also studied but ineffective to degrade PFC molecules. However, PFCs could be removed in aeration flow by another mechanism. / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第13340号 / 工博第2837号 / 新制||工||1417(附属図書館) / UT51-2007-M963 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 藤井 滋穂, 教授 伊藤 禎彦 / 学位規則第4条第1項該当 / Doctor of Engineering / Kyoto University / DFAM

This study aims to detect how many microplastics and what kind are released from the wastewater treatment plant (WWTP) Skebäck, in Örebro. The study was limited to the analysis of three filters with 50 μm mesh size and one filter with 300 μm mesh size. The samples were taken at different times, two in the fall of 2019 and one in the spring of 2020. Visual characterization was used for the quantification of microplastics, and a lower and upper bound was used. The lower bound represents particles that were deemed identifiable as plastic with high certainty, while the upper bound also includes particles that may have been microplastic. An additional ATR-FTIR analysis was performed on selected microplastics >300 μm.  The presence of microplastics in the effluent from Skebäcks WWTP could be confirmed. The quantity of microplastics per m​3​ (MP/m​3​) trapped on the 50 μm filters were quantified in a range between 0 MP/m​3​ to 291 MP/m​3​ for the lower bound, and 72 MP/m​3​ to 435 MP/m​3​ for the upper bound. The 300 μm filter had considerably less microplastics than the 50 μm filter with 1.8 MP/m​3​. The quantification of fibers on the 50 μm filter and 300 μm filters was not possible due to high blank contaminations. According to the concentration of 63 MP/m​3​ of the lower bound count on the 50 μm filters and the amount of water flowing through Skebäck in 2019, 17 818 935 m​3​, 1.1 billion microplastic particles were released into Svartån that year. In comparison the highest value of the upper bound count, 435 MP/m​3​, gave a release of 7.7 billion microplastic particles. Using the concentration of the 300 μm filter 1.8 MP/m​3​, 32 million microplastics/year were released from Skebäck in 2019. The amount of spheres 50-300 μm released in the effluent from Skebäck was estimated to be 3.7 kg in 2019.

The thesis is focused on the area of wastewater treatment. There is a solution possibility of using flotation for the removal of phosphorus precipitates formed during the tertiary treatment of wastewater. The first part is devoted to a general description of wastewater treatment, there is also described as a flotation separation technology and precipitation of phosphorus. The second part is practically oriented. It describes the experimental equipment used for the precipitation of phosphorus and subsequent removal of the precipitate flotation, during the experiment and the results obtained.

Att följa ammonium i reningsverk är avgörande för att förbättra reningsprocessen och kontrollera flödet av föroreningar ut till ekosystemet. Jonselektiva elektroder (ion-selective electrodes, ISEs) är en lovande teknik inom området, där polymermembran baserade på nonactin är de mest studerade membranen för ammoniumsensorer. Membranet droppas tillsammans med ett jon-till-elektron transducerande material på ett elektrodsubstrat av grafit eller glasartat kol. Nonactin-baserade jonselektiva elektroder har typiskt en detektionsgräns inom storleksordningen 10-5 M, men uppvisar betydande kaliuminterferenser. Ett elektrodsystem baserat på grafitelektroder, inkluderande en ISE och en referenselektrod (RE), studerades i detta examensarbete. De jonselektiva elektroderna producerades genom att droppa jon-till-elektron trandsducerande funktionella flerväggiga kolnanotuber (functional multiwalled carbon nanotubes, f-MWCNTs) lösta i tetrahydrofuran (THF) och en membrancocktail innehållande polyvinylklorid (PVC), mjukgörare och nonactin löst i THF på grafitelektroder. Membranet täcktes sedan med en buffrad polyvinylalkohol (PVA) hydrogel med pH 7 och ett gas-permeabelt membran. Referenselektroderna producerades genom att droppa en membrancocktail av polyvinylbutyral (PVB) mättat med NaCl på grafitelektroder. Jonselektiva elektroder med f-MWCNTs som jon-till-elektron transducerande lager och ett PVC-baserat ammonium-selektivt membran med nonactin producerades framgångsrikt. Elektroderna hade en detektionsgräns i storleksordningen 10-5 M, vilket kan jämföras med tidigare artiklar publicerade inom området. Ytterligare producerades PVB-baserade referenselektroder mättade med NaCl framgångsrikt. Referenselektroderna uppvisade små variationer när koncentrationer av olika salt varierades. Arbetet visade att det gaspermeabla membranet Hyflon AD i kombination med en PVA hydrogel inte var lämplig i den föreslagna konfigurationen, då hålrum formades i torkningsprocessen av det gaspermeabla membranet och membranet delaminerade. Det föreslogs att beteendet kunde vara en konsekvens av inkompatibilitet mellan PVC och det gaspermeable membranet, till följd av deras skillnad i polaritet. / Monitoring ammonium in wastewater is vital to improve the treatment process and monitor the release of the pollutant into the ecosystem. Ion-selective electrodes (ISEs) is a promising technique in the area where the ISE is often based on a polymeric membrane containing the ionophore nonactin. The polymeric ion-selective membrane is drop-cast onto graphite or glassy carbon electrode substrates together with an ion-to-electron transducing layer. Nonactin-based ISEs typically demonstrate a limit of detection (LOD) in the range of 10-5 M, but exhibit significant potassium interferences. A solid-state system based on graphite electrodes, including an ISE and a reference electrode (RE), was investigated in this study. The ISEs were produced by drop-casting ion-to-electron transducing functional multi-walled carbon nanotubes (f-MWCNTs) dispersed in tetrahydrofuran (THF) and a membrane cocktail comprising poly(vinyl chloride) (PVC), plasticizer, and nonactin dispersed in THF onto graphite electrodes. The membrane was then covered with a buffered poly(vinyl alcohol) (PVA) hydrogel of pH 7 and a gas-permeable membrane (GPM). The solid-state RE was produced by drop-casting a poly(vinyl butyral) (PVB) membrane cocktail saturated with NaCl onto the graphite electrode.  ISEs using f-MWCNTs as ion-to-electron transducers and a PVC-based ammonium-sensitive membrane with nonactin were successfully produced. The electrodes exhibited LODs in the range of 10-5 M, which is comparable to previous articles published on the subject. Additionally, PVB-based solid-state REs saturated with NaCl were successfully produced. The reference electrodes exhibited minor influences when varying the concentrations of various salts. The study showed that the GPM Hyflon AD combined with a PVA hydrogel was not suitable in this configuration, as air voids were formed in the drying process, and the membrane was easily delaminated. It was suggested that this behavior could be a consequence of the incompatibility of PVC and the GPM due to their difference in polarity.

The diploma thesis is focused on phosphorus recovery from sewage sludge. In the first part of the thesis, research of phosphorus recovery from sewage sludge is explained. Reusing of phosphorus, a critical material of mankind, is expressed with the principles of the circular economy. The second part of the thesis defines the potential of phosphorus extraction from sewage sludge from medium-sized (Trutnov WWTP) and large (Modřice WWTP) wastewater treatment plant and a technical and economic study of the proposed phosphorus recycling system at these wastewater treatment plants is described.

[ES] El uso del agua en nuestra sociedad es de gran importancia. Cuando el agua se utiliza y deja de ser útil, se convierte en agua residual. Esta contiene sustancias que ponen en peligro la salud humana y los ecosistemas. Para reducir el daño ambiental existen las depuradoras que reducen los niveles de contaminación del agua. En las industrias, las depuradoras se encargan de reducir la carga contaminante del agua para su vertido en alcantarillado o al medio ambiente. La presencia de vertidos ilegales y desbordamientos en el alcantarillado suponen una amenaza para las masas de agua. Estos provocan una bajada en el rendimiento de las depuradoras. En muchos casos no es posible detectar al responsable de estos. Lo que hace que estos queden impunes violando el principio ambiental de quien contamina paga. Para solucionar este problema se propone un sistema de bajo coste para la monitorización de parámetros del agua para detectar problemas en los alcantarillados dentro de las ciudades inteligentes (Smart cities). La hipótesis de trabajo es que ante la presencia de un vertido ciertos parámetros del agua cambiarán lo suficiente como para que pueda ser detectado. Al detectarse el sitio del vertido se podrá acudir rápidamente al lugar a fin de cesar el vertido además de tomar las acciones legales pertinentes. Primero, hemos estudiado otros sistemas para monitorizar el alcantarillado Con esta información se determina los parámetros más interesantes y que pueden ser medidos con un bajo coste son temperatura, conductividad, turbidez, nivel de agua y aceite. Además, de sensores de lluvia para el alcantarillado pluvial. Para la monitorización de estos parámetros se escogen sensores comerciales de bajo coste para los parámetros de temperatura, nivel y lluvia. Para los otros parámetros se decidió desarrollar nuestros propios sensores. Para ello se utilizó sensores del tipo inductivos para la conductividad y sensores ópticos para el control de la turbidez y el aceite. Respecto a los sensores inductivos, se ha determinado que existen interferencias de los sólidos y del nivel de agua en la respuesta del sensor. Sin embargo, en el caso de los sólidos esta interferencia es pequeña en la concentración de solidos que existe en el alcantarillado, siendo esta de 0.078 V/gramo. En cambio, la cantidad de agua sí que afecta a la respuesta de la bobina de forma significativa. Respecto a la turbidez se han realizado dos prototipos diferentes. Un prototipo ha sido desarrollado para cuerpos de agua y el otro para el alcantarillado. El prototipo desarrollado para cuerpos de agua es capaz de determinar el porcentaje de algas que existen en el agua conociendo la cantidad de solidos en el agua. Para la detección del aceite hemos desarrollado otro sensor óptico. Hemos hecho pruebas a distintas alturas de agua. Viendo que éramos capaces de identificar si el aceite provenía de un motor gasolina o de un motor diésel, y en el caso de aceite usado por un motor de gasolina éramos capaces de cuantificarlo. Por último, respecto a nuestro sistema hemos analizado mediante simulaciones la utilidad de un sensor de nivel en el alcantarillado. Hemos detectado que en el caso de alcantarillado pluvial este sí que puede ser útil. Además, hemos testeado en una tubería el sensor inductivo y el de aceite con diferentes concentraciones de sal y aceite para ver su funcionamiento. El coste estimado de cada uno de los nodos sensores es de 120 €. Los sensores desarrollados pueden ser utilizados en otros ambientes. Estos trabajos son: (I) el uso de bobinas para la monitorización de la humedad del suelo, (II) el uso de sensores ópticos para detectar gasóleo B en vehículos (III) el uso de sensores y tecnología de bioabsorción en canales de riego afectados por aguas residuales y (IV) el uso del sensor de aceite en canales de riego. / [CA] The use of water in our society is of great importance. Once the water has been used, it becomes wastewater. These waters contain substances that endanger human health and ecosystems. To reduce environmental damage, there are treatment plants that treat these waters to reduce their levels of contamination. Industrial treatment plants are responsible for reducing the contaminant load of the water so that it can be discharged into the public sewer system or into the environment. The presence of illegal discharges and overflows in the sewage system pose a threat to water bodies. These discharges can cause a drop in the performance of the treatment plant, which will cause an effluent of poorer quality. In many cases, it is not possible to detect who is responsible for the spills. What makes these go unpunished violating the environmental principle of that whoever pollutes pays. To solve this problem, a low-cost system for monitoring water parameters to detect problems in sewers within the context of smart cities is proposed. Our working hypothesis is that in the presence of a discharge, the concentration of specific water parameters will change enough to be detected. When the site of the spill is detected, it will be possible to quickly go to the place in order to stop the spill in addition to taking the necessary legal actions against the person who is carrying out the spill. First, we have compiled information about other systems to monitor sewage, With this information, we have determined that the most exciting parameters that we are able to measure at a low cost are temperature, conductivity, turbidity, water and oil level. In addition, the use of rain sensors for storm sewers is included. To monitor these parameters, low-cost commercial sensors are chosen to monitor temperature, level and rainfall. For the other parameters, we decided to develop our own sensors. We decided to use inductive type sensors for conductivity and optical sensors for turbidity and oil control. Regarding the inductive sensors, we have determined that there are interferences of the solids and the water level in the response of the sensor.. However, in the case of solids, this interference is minor in the concentration of solids that exists in the sewage system (0.078 V/gram). On the other hand, the amount of water does affect the response of the coil significantly. Therefore, the sensor must be submerged. Regarding turbidity, we have made two different prototypes. One prototype has been developed for bodies of water and the other for sewage. The prototype developed for bodies of water is capable of determining the percentage of algae that exist in the water, knowing the amount of solids in the water. For oil detection, we have developed another optical sensor. We have done tests at different heights of water. Seeing that we were able to identify if the oil came from a gasoline engine or a Diesel engine, and in the case of oil used by a gasoline engine, we were able to quantify it. Finally, regarding our system, we have analyzed through simulations the usefulness of a level sensor in the sewage system. We have detected that in the case of storm sewage, this can be useful. In addition, we have tested the inductive sensor and the oil sensor in a pipe with different concentrations of salt and oil to see how they work. The estimated cost of each sensor node is 120 €. The developed sensors can be used in other environments. For this reason, we show other works carried out during the thesis period with the developed sensors. These works are: (I) The use of coils for soil moisture monitoring, (II) the use of optical sensors to detect diesel B in vehicles, (III) the use of sensors and bioabsorption technology in irrigation canals affected by wastewater, and (IV) the use of the oil sensor in irrigation channels. / [EN] L'ús de l'aigua a la nostra societat és de gran importància. Un cop l'aigua s'ha utilitzat i deixa de ser útil per a l'activitat, aquesta es converteix en aigües residuals. Aquestes aigües contenen substàncies que posen en perill la salut humana i dels ecosistemes. Per reduir el danys mediambientals existeixen les depuradores que tracten aquestes aigües per reduir contaminació la seua carrega contaminants.. Les depuradores industrials s'encarreguen de reduir la càrrega contaminant de l'aigua perquè es pugui abocar al clavegueram públic o al medi ambient. La presència d'abocaments d'aigua il·legals i els desbordaments al clavegueram suposen una amenaça per a les masses d'aigua. Aquests abocaments poden provocar una baixada en el rendiment de la depuradora. En molts casos no és possible detectar el responsable dels abocaments. Això fa que aquests queden impunes violant el principi ambiental de qui contamina paga. Per solucionar aquest problema es proposa un sistema de baix cost per a la monitorització de l'aigua per detectar problemes als claveguerams en les ciutats intel·ligents (Smart cities). La hipòtesi de treball consisteix que davant la presència d'un abocament la concentració de certs paràmetres de l'aigua canviarà lo suficient perquè es pugui detectar. En detectar-se el lloc de l'abocament es podrà acudir ràpidament al lloc per cessar l'abocament a més de prendre les accions legals que siguin necessàries contra la persona que està realitzat l'abocament. Primer, hem estudiat altres sistemes per monitoritzar el clavegueram. Amb aquesta informació s'ha determinat que els paràmetres més interessants i que poden ser mesurats amb un baix cost són temperatura, conductivitat, terbolesa, nivell d'aigua i oli. A més, l'ús de sensors de pluja per al clavegueram de pluvials. Per monitoritzar aquests paràmetres s'escullen sensors comercials de baix cost per ala temperatura, el nivell i la pluja. Per als altres paràmetres, es decideix desenvolupar els nostres propis sensors. Decidim utilitzar sensors del tipus inductius per a la conductivitat i sensors òptics per al control de la terbolesa i l'oli. Pel que fa als sensors inductius, s'ha determinat que hi ha interferències dels sòlids i del nivell d'aigua en la resposta del sensor. No obstant això, en el cas dels sòlids aquesta interferència és petita en la concentració de sòlids que hi ha al clavegueram, aquesta és de 0.078 V/gram. En canvi, la quantitat d'aigua sí que afecta la resposta de la bobina de manera significativa. Pel que fa a la terbolesa s'han realitzat dos prototips diferents. Un prototip ha estat desenvolupat per a cossos d'aigua i l'altre per al clavegueram. El prototip desenvolupat per a cossos d'aigua és capaç de determinar el percentatge d'algues que hi ha a l'aigua coneixent la quantitat de sòlids a l'aigua. Per detectar l'oli hem desenvolupat un altre sensor òptic. Hem fet proves a diferents alçades d'aigua. Veient que érem capaços d'identificar si l'oli provenia d'un motor benzina o d'un motor dièsel, i en el cas d'oli usat per un motor de benzina érem capaços de quantificar-lo. Finalment, respecte al nostre sistema hem analitzat mitjançant simulacions la utilitat d'un sensor de nivell al clavegueram. Hem detectat que en el cas de clavegueram pluvial aquest sí que pot ser útil. A més, hem testejat en una canonada el sensor inductiu i el d'oli amb diferents concentracions de sal i oli per veure'n el funcionament. El cost estimat de cadascun dels nodes sensors és de 120 €. Els sensors desenvolupats poden ser utilitzats en altres ambients.. Aquests treballs són: (I) L'ús de bobines per a la monitorització de la humitat del sòl, (II) l'ús de sensors òptics per detectar gasoil B (sota impostos) en vehicles no autoritzats, (III) l'ús de sensors i tecnologia de bioabsorció en canals de reg afectats per aigües residuals, (IV) l'ús del sensor d'oli a canals de reg. / Rocher Morant, J. (2023). Study and Design of a Sensor System for the Detection of Illicit Discharges in Sewers and Water Bodies [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/192823