Leaching of soil salinity in irrigated and non-irrigated agriculture is crucial to ensure sustainable food production. Soil salinity is considered a global problem, since more than 800 million hectares (6% of the world's total area) worldwide are salt-affected. Generally, the regions affected by soil salinity also face water scarcity problems. Consequently, in these regions, even saline waters are considered to be essential resources for agriculture. The use of inefficient irrigation practices in regions that experience water scarcity, especially those using saline water, aggravates soil salinity problems. Therefore, in the context of these constraints and challenges, increasing the efficiency of water use for irrigation and leaching is necessary. An increasing interest in using drip irrigation systems (DI) is noticed in the current research that deals with water scarcity due to the benefits of applying water precisely in time and space. However, the traditional leaching guidelines, based on steady-state conditions, are not appropriate for DI. Therefore, the use of DI for leaching practices is still under question. The objectives of this study are (i) to better understand and assess the leaching process for common DI, and (ii) to develop a simulation-based optimization approach considering site-specific conditions for optimal DI design for salinity management. Accordingly, a new two-stage framework for optimizing leaching practices has been developed focusing on DI. The transient-state-based numerical model HYDRUS-2D was used for simulating water movement and solute transport processes for both stages. In the first stage, a general assessment tool for leaching practices in the form of “irrigation atlas” was created using two-dimensional (2D) numerical experiments. The atlas displays and compares the reclamation leaching results of (i) surface drip irrigation (SI), (ii) subsurface irrigation drip irrigation (SDI), (iii) sprinkler irrigation (S), and (iv) flood irrigation. The results are introduced graphically, showing the final 2D salinity distribution in the soil profile, and numerically giving the water and salt mass balances. The SI and SDI results show the high potential of these systems for improving the efficiency of salinity leaching. However, because of the resultant localized leaching patterns, the performance of these systems depends on the location of the drip line relative to the targeted leaching area. In the second stage of the study a site-specific optimization framework for leaching design and management was developed through a combination of simulation and optimization. The objective was to achieve optimal leaching results with a given limited amount of water. The framework was applied in synthetic field conditions for reclamation leaching in two and silt). Moreover, the framework was based on running numerous simulations of possible DI setups (scenarios). The optimization approach made it possible to derive values for the optimal irrigation design parameters for salinity management under the given field conditions. The new optimization framework was implemented in a case study focusing on the impact of different DI designs on yield and the leaching of salts. The framework aims to make the most effective use of an existing DI system by optimizing the combination of irrigation frequency, duration, and discharge. The optimization framework was successfully employed: (i) to increase the relative yield of the considered crop, and (ii) to reduce the subsurface drainage towards the saline and shallow groundwater, which contributes to better control of the saline groundwater levels in the study area. The seasonal results confirmed the leaching pattern of a dripper presented in the irrigation atlas. The optimal seasonal solutions are presented as site and crop specific leaching and water productivity functions for a wide range of applied water and different irrigation water salinities. The developed optimization framework proved to be a suitable approach for assessing and improving leaching management of DI under salinity conditions and deriving optimal design parameter values. The suitability and flexibility of the framework were verified through implementation in a case study with new field conditions and objectives, and it was shown that the reliability of the proposed framework depends on the quality of the collected and measured data required for the model inputs.

<p>Predmet izučavanja ove disertacije obuhvatio je ispitivanje uticaja starenja stabilizovanog/solidifikovanog&nbsp; (S/S)&nbsp; sedimenta&nbsp; zagađenog te&scaron;kim metalima i arsenom, i efikasnost primenjenih imobilizacionih agenasa (Portland cement, kreč, leteći pepeo, zeolit, montmorilonit i kaolinit) nakon dugogodi&scaron;njeg starenja S/S sme&scaron;a. Shodno tome ispitana je dugoročna stabilnost i postojanost dobijenih S/S sme&scaron;a sa aspekta izluživanja pomenutih metala, promene u minerolo&scaron;kim i strukturnim karakteristikama, kao i uticaj su&scaron;enja i zrenja materijala na pomenute parametre. Istraživanja u disertaciji obuhvatila su dve faze. Prva faza imala je za cilj procenu rizika i&nbsp; početnu karakterizaciju netretiranog sedimenta primenom analize pseudo-ukupnog sadržaja metala kojom je utvrđen sadržaj metala u početnom uzorku sedimenta. Druga faza uključivala je primenu tretmana stabilizacije i solidifikacije na kontaminirani sediment dodavanjem različitih imobilizacionih agenasa. Analize su se vr&scaron;ile nakon 7 i 28 dana od primenjenog S/S tretmana, kao i nakon 7 godina sa ciljem da se utvrdi uticaj vi&scaron;egodi&scaron;njeg starenja i zrenja monolitnih sme&scaron;a na mobilnost metala i strukturne karakteristike sme&scaron;a. U&nbsp; okviru&nbsp; druge faze istraživanja ispitana je toksičnost S/S sme&scaron;a primenom DIN i TCLP testova izluživanja, dok je test toksičnosti primenom bakterija Vibrio Fischeri&nbsp; doprineo u&nbsp; sagledavanju&nbsp; procene rizika S/S sme&scaron;a po organizme. Nakon 28 dana i 7 godina kori&scaron;ćena je sekvencijalna ekstrakcija za&nbsp; određivanje mobilnost i biodostupnost metala u monolitnim matriksima. U cilju&nbsp; utvrđivanja mikrostukturnih karakteristika sedimenta primenjena je rendgenska difrakciona analiza (XRD) za ispitivanje kristalnih struktura&nbsp; S/S sme&scaron;a i detekciju mineralnog sastava. Pomoću elektronskog mikroskopa i energodisperzivnog detektora&nbsp; sa X-zrakom (SEM/EDS) određena je kvalitativna i kvantitativna distribucija metala i&nbsp; drugih elemenata od interesa, dok se za identifikaciju formiranih funkcionalnih grupa u monolitnim sme&scaron;ama primenio spektrometar sa infracrvenom Furijeovom transformacijom (FTIR). Na osnovu dobijenih rezultata zaključeno je da se mobilnost te&scaron;kih metala i arsena značajno smanjila nakon 7 godina za sme&scaron;e tretirane cementom (C5), krečom (L10), letećim pepelom (F30) i kaolinitom&nbsp; (K20), a efekat stabilizacije je pokazan transformacijom metala iz direktne toksične frakcije u&nbsp; stabilnije oblike. Sme&scaron;e C5 i K20 ispoljavaju&nbsp; najmanje toksične efekate od svih sme&scaron;a, jer je procenat inhibicije&nbsp; na&nbsp; bioluminiscentnim&nbsp; bakterijama manji od 13%, dok je u pogledu izdržljivosti monolitna sme&scaron;a C5 pokazala najveću pritisnu čvrstoću od svih sme&scaron;a. Dobijeni podaci su neprocenjivi za dobijanje stvarnog uvida u dugoročnu efikasnost&nbsp; primenjenog&nbsp; tretmana i mogućnost bezbedne upotrebe ili odlaganja dobijenih S/S sme&scaron;a sa aspekta za&scaron;tite životne sredine, kao i ekonomski i ekolo&scaron;ki prihvatljivog upravljanja opasnim otpadom.</p> / <p>The subject of study in this dissertation included to investigate the&nbsp; effect&nbsp; of&nbsp; aging&nbsp; of&nbsp; stabilized/solidified&nbsp; (S/S)&nbsp; sediment&nbsp; contaminated with&nbsp; heavy&nbsp; metals&nbsp; and&nbsp; arsenic,&nbsp; and&nbsp; the&nbsp; efficacy&nbsp; of&nbsp; the&nbsp; applied immobilization&nbsp; agent&nbsp; (Portland&nbsp; cement,&nbsp; lime,&nbsp; fly&nbsp; ash,&nbsp; zeolite, montmorillonite and kaolinite) after long-term aging of S/S mixtures. The<br />long&nbsp; -&nbsp; term stability and stability of the obtained S/S mixtures from the aspect of leaching of the mentioned metals, changes in mineralogical and structural characteristics,&nbsp; as&nbsp; well&nbsp; as&nbsp; the&nbsp; influence&nbsp; of&nbsp; drying&nbsp; and maturation of the material on the mentioned parameters were examined. The&nbsp; research&nbsp; in&nbsp; the&nbsp; dissertation&nbsp; included&nbsp; two&nbsp; phases.&nbsp; The&nbsp; first&nbsp; phase aimed&nbsp; at&nbsp; risk&nbsp; assessment&nbsp; and&nbsp; initial characterization&nbsp; of&nbsp; untreated sediment using pseudo-total metal content analysis which determined the<br />metal content in the initial sediment sample.&nbsp; The second phase involved applying&nbsp; stabilization&nbsp; and&nbsp; solidification&nbsp; treatments&nbsp; to&nbsp; the&nbsp; contaminated sediment&nbsp; by&nbsp; adding&nbsp; various&nbsp; immobilizing&nbsp; agents.&nbsp; The&nbsp; analyzes&nbsp; were performed after 7 and 28&nbsp; days from the applied S/S treatment, as well as after 7 years in order to determine the influence of perennial aging and maturation&nbsp; of&nbsp; monolithic&nbsp; mixtures&nbsp; on&nbsp; metal&nbsp; mobility&nbsp; and&nbsp; structural characteristics&nbsp; of&nbsp; the&nbsp; mixtures.&nbsp; In&nbsp; the&nbsp; second&nbsp; phase&nbsp; of&nbsp; the&nbsp; study,&nbsp; the toxicity&nbsp; of&nbsp; S/S&nbsp; mixtures&nbsp; using&nbsp; DIN&nbsp; and&nbsp; TCLP&nbsp; leaching&nbsp; tests&nbsp; was examined, while&nbsp; the&nbsp; toxicity&nbsp; test&nbsp; using&nbsp; bacteria&nbsp; Vibrio&nbsp; Fischeri contributed&nbsp; to&nbsp; the assessment&nbsp; of&nbsp; the&nbsp; risk&nbsp; of&nbsp; S/S&nbsp; mixtures&nbsp; to&nbsp; organisms. After&nbsp; 28 days&nbsp; and&nbsp; 7 years,&nbsp; sequential extraction was&nbsp; used to&nbsp; determine the mobility and bioavailability of metals in monolithic matrices. In order to&nbsp; determine&nbsp; the&nbsp; microstructural&nbsp; characteristics&nbsp; of&nbsp; the&nbsp; sediment,&nbsp; x-ray diffraction analysis (XRD) was used to examine the crystal structures of&nbsp; S/S mixtures and&nbsp; to detect the mineral composition.&nbsp; The qualitative and quantitative&nbsp; distribution&nbsp; of&nbsp; metals&nbsp; and&nbsp; other&nbsp; elements&nbsp; of&nbsp; interest&nbsp; was determined using an electron microscope and an energy-dispersive X-ray detector&nbsp; (SEM&nbsp; /&nbsp; EDS),&nbsp; while&nbsp; an&nbsp; infrared&nbsp; Fourier&nbsp; transform spectrometer(FTIR) was used to identify the formed functional groups in monolithic mixtures. Based on the obtained results, it was concluded that the mobility of heavy metals and arsenic decreased significantly after 7 years&nbsp; for&nbsp; mixtures&nbsp; treated&nbsp; with&nbsp; cement&nbsp; (C5),&nbsp; lime&nbsp; (L10),&nbsp; fly ash&nbsp; (F30) and&nbsp; kaolinite&nbsp; (K20),&nbsp; and&nbsp; the&nbsp; stabilization&nbsp; effect&nbsp; was&nbsp; shown&nbsp; by transformation&nbsp; of&nbsp; metals&nbsp; from&nbsp; direct&nbsp; toxic&nbsp; fractions&nbsp; into&nbsp; more&nbsp; stable forms. Mixtures&nbsp; C5&nbsp; and&nbsp; K20&nbsp; exhibit&nbsp; the&nbsp; least&nbsp; toxic&nbsp; effects&nbsp; of&nbsp; all mixtures, because the percentage of inhibition on bioluminescent bacteria is less than 13%, while in terms of durability, the monolithic mixture C5 showed&nbsp; the&nbsp; highest&nbsp; compressive&nbsp; strength&nbsp; of&nbsp; all&nbsp; mixtures.&nbsp; The&nbsp; obtained data are invaluable for gaining real insight into the long-term efficiency of the applied treatment and the possibility of safe use&nbsp; or disposal of the obtained&nbsp; S/S&nbsp; mixtures&nbsp; from&nbsp; the&nbsp; aspect&nbsp; of&nbsp; environmental&nbsp; protection,&nbsp; as well&nbsp; as&nbsp; economically&nbsp; and&nbsp; ecologically&nbsp; acceptable&nbsp; hazardous&nbsp; waste management.</p>

付記する学位プログラム名: グローバル生存学大学院連携プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第21465号 / 農博第2308号 / 新制||農||1064(附属図書館) / 学位論文||H31||N5160(農学部図書室) / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 舟川 晋也, 教授 間藤 徹, 教授 縄田 栄治 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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В данной работе проведено исследование переработки мышьяксодержащих шламов нейтрализации отработанных электролитов с целью селективного извлечения ценных металлов (медь, никель). Для определения химического и фазового анализа техногенного многокомпонентного сырья применены методы спектрофотометрии (AAС) и рентгенофазовой дифрактоскопии. Предложен выщелачивающий комплексообразующий реагент Трилон Б и обоснован его выбор. Проведены литературный обзор современных методов переработки, лабораторные исследования. Исследованы и оптимизированы процессы выщелачивания шламов водным раствором Трилона Б, очистки полученного трилонатного раствора от металлов-примесей, регенерации растворителя. Так же в диссертации выбрана оптимальная схема переработки гидроксидных шламов и отражено эколого-экономическое обоснование выбранной технологии переработки. / In this paper, research arsenic-containing slimes of neutralization of waste electrolytes was carried out to selectively extract valuable metals (copper, nickel). The method of Atomic Absorption Spectroscopy (AAS), X-ray Diffraction (XRD) was applied. The chemical and phase analysis of multicomponent manmade waster was carried out, the leaching chelating reagent Trilon B was offered and its choice is reasonable. A review of modern methods of processing and laboratory studies were carried out. The processes of leaching of slimes by aqueous solution of Trilon B, purification of the obtained trilonate solution from metal-impurities and solvent regeneration were studied and optimized. Also, in the thesis the optimal scheme of processing of hydroxide sludges was chosen and the ecological and economic justification of the chosen technology of processing was represented.

Целью ВКР является разработка процесса извлечения цветных металлов из гальванического шлама. Предложен вариант аммиачного растворения гальванического шлама, обеспечивающий селективный перевод в раствор никеля. Изучено сорбционное поведение никеля в сернокислых и аммиачных растворах. / The object of this work is to develop the process of extraction of non-ferrous metals from galvanic sludge. The variant of electroplating sludge leaching by ammonium solution, providing selective transfer of nickel in solution is proposed. Sorption behavior of nickel in sulfuric acid and ammonia solutions was studied.

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[pt] O aumento do consumo de eletroeletrônicos e o desenvolvimento da tecnologia, proporcionou o surgimento de uma gama de produtos com diferentes funcionalidades, cada vez mais complexos e menores. As placas de circuito impresso (PCIs) são consideradas a parte principal dos dispositivos eletrônicos, sendo o cobre o seu componente elementar. O desenho e espessura das trilhas do circuito são determinantes para caracterizar a passagem de corrente elétrica nos equipamentos eletroeletrônicos e seu funcionamento está diretamente ligado a qualidade da confecção das trilhas do circuito. Este trabalho tem como objetivo estudar o processo de lixiviação do cobre, mediante a reação do ácido clorídrico, cloreto de cobre II e fluxo de ar. Além de investigar as condições experimentais ótimas do processo, que tem como principal característica a possibilidade de regeneração e reutilização da solução. Modelos para avaliar o efeito da concentração de ácido e fluxo de ar na corrosão das placas de circuito impresso foram desenvolvidos através da aplicação do planejamento experimental (pelo método clássico e por algoritmo genéticos em modelos polinomiais) e redes neurais artificiais. Visando encontrar as melhores condições experimentais para o sistema proposto, além de investigar a melhor técnica de predição do mesmo. Os resultados obtidos pelas previsões foram comparados com os resultados experimentais reais. As modelagens foram comparadas pela análise dos coeficientes de correlação (R2) e índices de erro (SSE, MSE e RMSE). Constatando-se que o modelo polinomial foi o mais adequado para prever a resposta. Através da investigação da superfície de resposta e curvas de contorno, foram identificadas as condições otimizadas para o processo. Das quais as concentrações ótimas de ácido clorídrico, cloreto de cobre II e fluxo de ar foram 1 mol.L-1, 0.3 mol.L-1 e 0.5 L/ min, respectivamente. / [en] The increased consumption of consumer electronics and the development of technology has led to the emergence of a range of products with different features, increasingly complex and smaller. Printed circuit boards (PCIs) are considered the main part of electronic devices, with copper being their elementary component. The design and thickness of the circuit tracks are crucial to characterize the passage of electric current in electronic equipment and its operation is directly linked to the quality of the circuit tracks. This work aims to study the copper leaching process through the reaction of hydrochloric acid, copper chloride II and airflow. In addition to investigating the optimal experimental conditions of the process, which has as its main feature the possibility of regeneration and reuse of the solution. Models to evaluate the effect of acid concentration and airflow on PCB corrosion were developed by applying experimental design (by the classical method and by the genetic algorithm in polynomial models) and artificial neural networks. Aiming to find the best experimental conditions for the proposed system, besides investigating the best prediction technique. The results obtained by the predictions were compared with the actual experimental results. The modeling was compared by analysis of correlation coefficients (R2) and error indices (SSE, MSE, and RMSE). Noting that the polynomial model was the most appropriate to predict the response. Through investigation of the response surface and contour curves, the optimized conditions for the process were identified. Of which the optimal concentrations of hydrochloric acid, copper chloride II and airflow were 1 mol.L-1, 0.3 mol.L-1 and 0.5 L / min, respectively.

Doctor of Philosophy / Rare earth elements (REEs) play a significant role in industrial production. Currently, much effort has been made to recover REEs from clays isolated from mining wastes such as coal byproducts. However, the concentrations of REEs in those clayey waste materials are too low, and they are not amenable to leaching even using strong acids. The developed extraction techniques usually need to be carried out at elevated temperatures (e.g., >100 oC) and consume substantial amounts of chemicals, which are not cost-effective and environmentally friendly. Given the issues, this study proposed a novel leaching technology that can recover REEs from clayey waste materials under mild conditions (<100 oC). Firstly, to simulate the recovery of REEs from coal-based clay materials, a monazite sample was pretreated with caustic soda (i.e., NaOH) at 80 oC for 24 h to convert the difficult-to-dissolve REEs (i.e., rare earth phosphate) into readily soluble forms (rare earth hydroxide), after which they were dissolved in 0.5 M ammonium sulfate solution at pH 4 and room temperature. A conceptual model was developed to explain the leaching mechanism of ammonium sulfate, which was found to be an ion exchange process. The proposed leaching process was also used to extract REEs from clay materials isolated from coal-based clay samples. A chelating ligand named ethylenediaminetetraacetic acid (i.e., EDTA) was added to the dilute NaOH solutions to reduce the alkali consumption during NaOH pretreatment. It was found that the presence of EDTA can improve the performance of NaOH pretreatment. Additionally, the content of REEs in a kaolinite waste material was physically upgraded to 10,765 ppm with ~72% recovery using a novel separation technique called hydrophobic-hydrophilic separation (HHS). The NaOH pretreatment and ammonium sulfate leaching process can also effectively recover REEs from the concentrate. The proposed leaching technology in this study can extract REEs from other low-grade clayey waste materials under mild conditions, which helps reduce wastewater generation and energy consumption. Furthermore, it will relieve the supply risk of REEs in the future.