Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Effects of anthropogenic and natural hydrological changes on the behavior of the acidic metal discharge from acid sulfate soils in a river- and lake system in western Finland

Larsmo-Öjasjön i Österbotten skapades genom invallningar på 1960-talet pga. industrins behov av sötvatten. Sedan dess har vattenområdet drabbats av återkommande försurning och fiskdöd, och invallningen har ofta beskyllts för problemen. Avhandlingen undersöker syrabelastningen i området; bl.a. hur markanvändning, hydrologi och klimatförändringen påverkar belastningen. Konsekvenserna undersöks med fiskyngel som bioindikator, och olika miljömetoder testas och diskuteras. Ökad kunskap om försurningen hjälper oss att tillämpa effektiva miljömetoder och få förbättrad vattenkvalitet i framtiden. Den primära orsaken till den försämrade vattenkvaliteten under de senaste 40 åren är intensiv dikning av svavelrika sediment. Detta leder till oxidering av svavlet till svavelsyra och uppkomst av sura sulfatjordar. Syran löser upp mängder med toxiska metaller som spolas ut i vattendragen. Undersökningen visar att tiotusentals ton svavelsyra tillsammans med stora mängder metaller rinner till Larsmo-Öjasjön per år från sura sulfatjordar. Åarna bidrar med mest belastning, men den sammanlagda belastningen från de otaliga dikena och bäckarna är oväntat stor. Andra potentiella källor till försurningen, t.ex. muddringar och humussyror, beräknas vara obetydliga. Syra- och metallbelastningen varierar kraftigt med hydrologin, dvs. störst belastning sker under vår- och höstflöden. En eventuell klimatförändring kan ändra på avrinningsmönstret och orsaka mera belastning vintertid. Den årligt återkommande syra- och metallbelastningen kan ofta hindra lakens förökning, vilket kan ha större långtgående konsekvenser för fiskpopulationerna än de relativt sällsynta stora surchockerna med synlig fiskdöd. För att förebygga skador på vattendragen bör man undvika att dränera svavelrika sedimenten. På redan existerande sura sulfatjordar visade sig kontroll av grundvattennivån kunna möjliggöra en effektiverad markanvändning utan märkbart ökade miljökonsekvenser.

Combination of pulsed corona discharge with TiO2 photocatalysis: verification of hypothesis

The oxidation potential of pulsed corona discharge concerning aqueous impurities is limited in respect to certain refractory compounds. This may be enhanced in combination of the discharge with catalysis/photocatalysis as developed in homogeneous gas-phase reactions. The objective of the work consists of testing the hypothesis of oxidation potential enhancement in combination of the discharge with TiO2 photocatalysis applied to aqueous solutions of refractory oxalate. Meglumine acridone acetate was included for meeting the practical needs. The experimental research was undertaken into oxidation of aqueous solutions under conditions of various target pollutant concentrations, pH and the pulse repetition rate with plain electrodes and the electrodes with TiO2 attached to their surface. The results showed no positive influence of the photocatalyst, the pollutants were oxidized with the rate identical within the accuracy of measurements. The possible explanation for the observed inefficiency may include low UV irradiance, screening effect of water and generally low oxidation rate in photocatalytic reactions. Further studies might include combination of electric discharge with ozone decomposition/radical formation catalysts.

Development of remote monitoring process tools for biomass fired bubbling fluidized bed boilers

Remote monitoring of a power boiler allows the supplying company to make sure that equipment is used as supposed to and gives a good chance for process optimization. This improves co-operation between the supplier and the customer and creates an aura of trust that helps securing future contracts. Remote monitoring is already in use with recovery boilers but the goal is to expand especially to biomass-fired BFB-boilers. To make remote monitoring possible, data has to be measured reliably on site and the link between the power plant and supplying company’s server has to work reliably. Data can be gathered either with the supplier’s sensors or with measurements originally installed in the power plant if the plant in question is not originally built by the supplying company. Main goal in remote monitoring is process optimization and avoiding unnecessary accidents. This can be achieved for instance by following the efficiency curves and fouling in different parts of the process and comparing them to past values. The final amount of calculations depends on the amount of data gathered. Sudden changes in efficiency or fouling require further notice and in such a case it’s important that dialogue toward the power plant in question also works.

Along-scan radiometric gradient in Landsat images: understanding the relation between floristic and remote sensing information in tropical forests

The along-scan radiometric gradient causes severe interpretation problems in Landsat images of tropical forests. It creates a decreasing trend in pixel values with the column number of the image. In practical applications it has been corrected assuming the trend to be linear within structurally similar forests. This has improved the relation between floristic and remote sensing information, but just in some cases. I use 3 Landsat images and 105 floristic inventories to test the assumption of linearity, and to examine how the gradient and linear corrections affect the relation between floristic and Landsat data. Results suggest the gradient to be linear in infrared bands. Also, the relation between floristic and Landsat data could be conditioned by the distribution of the sampling sites and the direction in which images are mosaicked. Additionally, there seems to be a conjunction between the radiometric gradient and a natural east-west vegetation gradient common in Western Amazonia. This conjunction might have enhanced artificially correlations between field and remotely-sensed information in previous studies. Linear corrections may remove such artificial enhancement, but along with true and relevant spectral information about floristic patterns, because they can´t separate the radiometric gradient from a natural one.

Fluvio-morphological processes of meander bends - Combining conventional field measurements, close-range remote sensing and computational modelling

Meandering rivers have been perceived to evolve rather similarly around the world independently of the location or size of the river. Despite the many consistent processes and characteristics they have also been noted to show complex and unique sets of fluviomorphological processes in which local factors play important role. These complex interactions of flow and morphology affect notably the development of the river. Comprehensive and fundamental field, flume and theoretically based studies of fluviomorphological processes in meandering rivers have been carried out especially during the latter part of the 20th century. However, as these studies have been carried out with traditional field measurements techniques their spatial and temporal resolution is not competitive to the level achievable today. The hypothesis of this study is that, by exploiting e increased spatial and temporal resolution of the data, achieved by combining conventional field measurements with a range of modern technologies, will provide new insights to the spatial patterns of the flow-sediment interaction in meandering streams, which have perceived to show notable variation in space and time. This thesis shows how the modern technologies can be combined to derive very high spatial and temporal resolution data on fluvio-morphological processes over meander bends. The flow structure over the bends is recorded in situ using acoustic Doppler current profiler (ADCP) and the spatial and temporal resolution of the flow data is enhanced using 2D and 3D CFD over various meander bends. The CFD are also exploited to simulate sediment transport. Multi-temporal terrestrial laser scanning (TLS), mobile laser scanning (MLS) and echo sounding data are used to measure the flow-based changes and formations over meander bends and to build the computational models. The spatial patterns of erosion and deposition over meander bends are analysed relative to the measured and modelled flow field and sediment transport. The results are compared with the classic theories of the processes in meander bends. Mainly, the results of this study follow well the existing theories and results of previous studies. However, some new insights regarding to the spatial and temporal patterns of the flow-sediment interaction in a natural sand-bed meander bend are provided. The results of this study show the advantages of the rapid and detailed measurements techniques and the achieved spatial and temporal resolution provided by CFD, unachievable with field measurements. The thesis also discusses the limitations which remain in the measurement and modelling methods and in understanding of fluvial geomorphology of meander bends. Further, the hydro- and morphodynamic models’ sensitivity to user-defined parameters is tested, and the modelling results are assessed against detailed field measurement. The study is implemented in the meandering sub-Arctic Pulmanki River in Finland. The river is unregulated and sand-bed and major morphological changes occur annually on the meander point bars, which are inundated only during the snow-melt-induced spring floods. The outcome of this study applies to sandbed meandering rivers in regions where normally one significant flood event occurs annually, such as Arctic areas with snow-melt induced spring floods, and where the point bars of the meander bends are inundated only during the flood events.

Formation of nitrates in water in presence of formate and oxalate treated with pulsed corona discharge (PCD)

Tavallisten hapetusmenetelmien sijasta kehittyneitä hapetusmenetelmiä (AOP) on kehitetty yhä enemmän, jotta hapetusprosessista tulisi kannattavampi, tehokkaampi, ympäristöystävällisempi ja sitä voitaisiin hyödyntää laajalti eri paikoissa. Uusi teknologia, joka käyttää otsonia ja hydroksyyliradikaalia sähköimpulssien kanssa, on yksi mahdollinen tehokkaampi vedenkäsittelymentelmä. Kyseistä menetelmää kutsutaa pulsed corona discharge (PCD) -menetelmäksi, joka käyttää prosessissa muodostuvia otsonia ja hydroksyyliradikaalia hapettavina tekijöinä. Tässä työssä tutkittiin nitraatin muodostumista vedessä, kun vettä käsiteltiin PCD-laitteessa ja, kun oksalaatti- ja formaatti-ioneja oli sekoittuneina veteen. Nitraatteja muodostuu PCD–laitteessa veteen, kun ilman typpi reagoi hapettimina toimivien otsonin ja hydroksyyliradikaalin kanssa. Aiemmissa tutkimuksissa nitraatin muodostumisen on todistettu parantuvan, kun karboksyylihapot muurahais- ja oksaalihappo ovat sekoittuneina veteen. Tässä tutkimuksessa tarkoituksena oli tutkia, miten formaatti- ja oksalaatti-ionien, joiden pitoisuudet olivat 0 ppm, 50 ppm ja 100 ppm, läsnäolo vedessä vaikuttaa nitraatin muodostumiseen. PCD-kokeista saadut näytteet analysoitiin ionikromatografilla. Kyseisessä tutkimuksessa nitraatin muodostuminen oli samansuuruista jokaisessa kokeessa hapetusajan kasvaessa samalla, kun otettujen näytteiden pH-arvot laskivat. Tuloksena voitiin pitää sitä, ettei formaatti- tai oksalaatti-ioneilla ollut vaikutusta nitraatti-ionien muodostumiseen.

Remote sensing for three-dimensional modelling of hydromorphology

Successful management of rivers requires an understanding of the fluvial processes that govern them. This, in turn cannot be achieved without a means of quantifying their geomorphology and hydrology and the spatio-temporal interactions between them, that is, their hydromorphology. For a long time, it has been laborious and time-consuming to measure river topography, especially in the submerged part of the channel. The measurement of the flow field has been challenging as well, and hence, such measurements have long been sparse in natural environments. Technological advancements in the field of remote sensing in the recent years have opened up new possibilities for capturing synoptic information on river environments. This thesis presents new developments in fluvial remote sensing of both topography and water flow. A set of close-range remote sensing methods is employed to eventually construct a high-resolution unified empirical hydromorphological model, that is, river channel and floodplain topography and three-dimensional areal flow field. Empirical as well as hydraulic theory-based optical remote sensing methods are tested and evaluated using normal colour aerial photographs and sonar calibration and reference measurements on a rocky-bed sub-Arctic river. The empirical optical bathymetry model is developed further by the introduction of a deep-water radiance parameter estimation algorithm that extends the field of application of the model to shallow streams. The effect of this parameter on the model is also assessed in a study of a sandy-bed sub-Arctic river using close-range high-resolution aerial photography, presenting one of the first examples of fluvial bathymetry modelling from unmanned aerial vehicles (UAV). Further close-range remote sensing methods are added to complete the topography integrating the river bed with the floodplain to create a seamless high-resolution topography. Boat- cart- and backpack-based mobile laser scanning (MLS) are used to measure the topography of the dry part of the channel at a high resolution and accuracy. Multitemporal MLS is evaluated along with UAV-based photogrammetry against terrestrial laser scanning reference data and merged with UAV-based bathymetry to create a two-year series of seamless digital terrain models. These allow the evaluation of the methodology for conducting high-resolution change analysis of the entire channel. The remote sensing based model of hydromorphology is completed by a new methodology for mapping the flow field in 3D. An acoustic Doppler current profiler (ADCP) is deployed on a remote-controlled boat with a survey-grade global navigation satellite system (GNSS) receiver, allowing the positioning of the areally sampled 3D flow vectors in 3D space as a point cloud and its interpolation into a 3D matrix allows a quantitative volumetric flow analysis. Multitemporal areal 3D flow field data show the evolution of the flow field during a snow-melt flood event. The combination of the underwater and dry topography with the flow field yields a compete model of river hydromorphology at the reach scale.

A new & accurate map of the North Pole with all the countries hitherto discovered situated near or adjacent to it as well as some others more remote. Drawn from the latest and best authorities and regulated by astronom.l observat.ns by Eman. Bowen.

0-meridiaani: Lontoo. - Koordinaattiasteikko: N90°-55°[50°].

Sensor communication in Smart cities and regions: An efficient IoT-based remote health monitoring system

Recent advances in Information and Communication Technology (ICT), especially those related to the Internet of Things (IoT), are facilitating smart regions. Among many services that a smart region can offer, remote health monitoring is a typical application of IoT paradigm. It offers the ability to continuously monitor and collect health-related data from a person, and transmit the data to a remote entity (for example, a healthcare service provider) for further processing and knowledge extraction. An IoT-based remote health monitoring system can be beneficial in rural areas belonging to the smart region where people have limited access to regular healthcare services. The same system can be beneficial in urban areas where hospitals can be overcrowded and where it may take substantial time to avail healthcare. However, this system may generate a large amount of data. In order to realize an efficient IoT-based remote health monitoring system, it is imperative to study the network communication needs of such a system; in particular the bandwidth requirements and the volume of generated data. The thesis studies a commercial product for remote health monitoring in Skellefteå, Sweden. Based on the results obtained via the commercial product, the thesis identified the key network-related requirements of a typical remote health monitoring system in terms of real-time event update, bandwidth requirements and data generation. Furthermore, the thesis has proposed an architecture called IReHMo - an IoT-based remote health monitoring architecture. This architecture allows users to incorporate several types of IoT devices to extend the sensing capabilities of the system. Using IReHMo, several IoT communication protocols such as HTTP, MQTT and CoAP has been evaluated and compared against each other. Results showed that CoAP is the most efficient protocol to transmit small size healthcare data to the remote servers. The combination of IReHMo and CoAP significantly reduced the required bandwidth as well as the volume of generated data (up to 56 percent) compared to the commercial product. Finally, the thesis conducted a scalability analysis, to determine the feasibility of deploying the combination of IReHMo and CoAP in large numbers in regions in north Sweden.

Underwater Remote Welding Technology for Offshore Structures

The construction of offshore structures, equipment and devices requires a high level of mechanical reliability in terms of strength, toughness and ductility. One major site for mechanical failure, the weld joint region, needs particularly careful examination, and weld joint quality has become a major focus of research in recent times. Underwater welding carried out offshore faces specific challenges affecting the mechanical reliability of constructions completed underwater. The focus of this thesis is on improvement of weld quality of underwater welding using control theory. This research work identifies ways of optimizing the welding process parameters of flux cored arc welding (FCAW) during underwater welding so as to achieve desired weld bead geometry when welding in a water environment. The weld bead geometry has no known linear relationship with the welding process parameters, which makes it difficult to determine a satisfactory weld quality. However, good weld bead geometry is achievable by controlling the welding process parameters. The doctoral dissertation comprises two sections. The first part introduces the topic of the research, discusses the mechanisms of underwater welding and examines the effect of the water environment on the weld quality of wet welding. The second part comprises four research papers examining different aspects of underwater wet welding and its control and optimization. Issues considered include the effects of welding process parameters on weld bead geometry, optimization of FCAW process parameters, and design of a control system for the purpose of achieving a desired bead geometry that can ensure a high level of mechanical reliability in welded joints of offshore structures. Artificial neural network systems and a fuzzy logic controller, which are incorporated in the control system design, and a hybrid of fuzzy and PID controllers are the major control dynamics used. This study contributes to knowledge of possible solutions for achieving similar high weld quality in underwater wet welding as found with welding in air. The study shows that carefully selected steels with very low carbon equivalent and proper control of the welding process parameters are essential in achieving good weld quality. The study provides a platform for further research in underwater welding. It promotes increased awareness of the need to improve the quality of underwater welding for offshore industries and thus minimize the risk of structural defects resulting from poor weld quality.

Oxidation of Aqueous Thiosulfate Solutions by Pulsed Corona Discharge

The aim of this Master’s thesis focused on the oxidation of sodium thiosulfate using non thermal plasma technology as an advance oxidation process (AOP). By using this technology we can degrade certain toxic chemical compounds present in mining wastewaters as pollutants. Different concentrations of thiosulfate and pulse frequencies were used in the PCD experiments and the results in terms of various delivered energies (kWh/m3) and degradation kinetics were compared. Pulsed corona discharge is an energy efficient process compared to other oxidation processes using for the treatment of waste water pollutants. Due to its simplicity and low energy costs make it attractive in the field of waste water treatment processes. This technology of wastewater treatment has been tested mainly on pilot scale level and in future the attempts are to be focus on PCD investigations on larger process scale. In this research work of oxidation of thiosulfate using pulsed corona discharge, the main aim of this research was to study degradation of a studied toxic and not environmental friendly chemical compound. The focus of this research was to study the waste waters coming from the gold mines containing leachate compound thiosulfate. Literature review contained also gold leaching process when cyanide is used as the leachate. Another objective of this work was to compare PCD process with other processes based on their energy efficiencies. In the experimental part two concentrations of sodium thiosulfate, 1000ppm and 400ppm, were used. Two pulse generator frequencies of 833 and 200 pulses per second (pps) were used. The chemical analyses of the samples taken during semi-batch PCD oxidation process were analyzed by ion chromatographic (IC). It is observed after the analyses that among different frequencies and concentrations, the most suitable ones for the process is 200pps and 1000ppm respectively because the pollutants present in the waste water has more time to react with the OH radicals which are the oxidants and the process is energy efficient compared to other frequencies.

Remote Observation of Radioactive Permit-Required Confined Spaces – Case: Posiva Oy’s Fuel Handling Cell

Posiva Oy’s final disposal facility’s encapsulation plant will start to operate in the 2020s. Once the operation starts, the facility is designed to run more than a hundred years. The encapsulation plant will be first of its kind in the world, being part of the solution to solve a global issue of final disposal of nuclear waste. In the encapsulation plant’s fuel handling cell the spent nuclear fuel will be processed to be deposited into the Finnish bedrock, into ONKALO. In the fuel handling cell, the environment is highly radioactive forming a permit-required enclosed space. Remote observation is needed in order to monitor the fuel handling process. The purpose of this thesis is to map (Part I) and compare (Part II) remote observation methods to observe Posiva Oy’s fuel handling cell’s process, and provide a possible theoretical solution for this case. Secondary purpose for this thesis is to provide resources for other remote observation cases, as well as to inform about possible future technology to enable readiness in the design of the encapsulation plant. The approach was to theoretically analyze the mapped remote observation methods. Firstly, the methods were filtered by three environmental challenges. These are the high levels of radiation, the permit-required confined space and the hundred year timespan. Secondly, the most promising methods were selected by the experts designing the facility. Thirdly, a customized feasibility analysis was created and performed on the selected methods to rank the methods with scores. The results are the mapped methods and the feasibility analysis scores. The three highest scoring methods were radiation tolerant camera, fiberscope and audio feed. A combination of these three methods was given as a possible theoretical solution for this case. As this case is first in the world, remote observation methods for it had not been thoroughly researched. The findings in this thesis will act as initial data for the design of the fuel handling cell’s remote observation systems and can potentially effect on the overall design of the facility by providing unique and case specific information. In addition, this thesis could provide resources for other remote observation cases.