Dissertations / Theses on the topic 'Pollutant waste'

This thesis presents the development of a numerical model for one-dimensional pollutant transport in a porous medium. A computer program POLUTE1D has been developed. The numerical model is based on the flow and mass transport equations and the finite element method has been used for its formulation. The problem involves unsaturated flow and convective dispersive transport of a contaminant species. A literature survey on the evaluation of the dispersion coefficient is included. A waste disposal dump site is analysed as a one-dimensional problem by using this model. The effect of the liner thickness, the liner permeability, the ponding head and the initial condition of the porous domain on the spread of the contaminant is studied. Conclusions are presented based on a parametric study.
M. Eng.

Landfill is continued to be the most common approach to solid waste disposal. On contrary, landfill practice is still common with increase in water pollution due to leaching of pollutants.Leachate generation from landfill can be defined into two phases, firstly soluble salt produced due to aerobic decomposition or acetogenic phase and secondly methane and carbon dioxide due to anaerobic decomposition or methanogenic phase.Characterization of landfill leachate is used in design to achieve low hydraulic conductivity or decrease permeability as leachate percolating through the waste strata and most important is used to predict level of pollutant in leachate which depend on factors such as temperature, precipitation and waste age. It is therefore crucial for landfill design to take into consideration of factors affecting leachate quality.The purpose of this research is to develop a correlation relationship of factors affecting leachate quality to predict pollutants from landfill which are determined by temperature, precipitation and waste age. The objective of this research is to determine, based the relationship developed and calibration of data obtained from literature review, the optimization of design that reduce pollutants in leachate generated from landfill taking into consideration of basic factors of temperature, precipitation and waste age of landfill.Results of the study revealed that there is a good correlation of pollutants leaching from landfill to the factors of temperature, precipitation and waste age. Higher pollutant concentration is found in average age landfill than the mature age landfill site mainly due to transition from acetogenic phase to methanogenic phase of pollutant decomposition. It is also anticipated that as carbonaceous organic matter decrease in leachate, nitrogeneous organic matter removal is activated in the mature landfill.Using Multiple Regression Analysis Method, mathematic model known as Pollutant Prediction Model is developed to correlate relationship of pollutants to factor affecting leachate quality in the landfill site in terms of temperature, precipitation and waste age.

The emission of metals during municipal solid waste incineration has become a question of considerable public and scientific concern in the light of evidence of their extreme toxicity. Sophisticated and expensive gas cleaning systems are required to meet the increasingly stringent EC atmospheric emission limits. While the technology for the clean-up of particulate matter and acid gases in flue gas is comparatively straightforward, the emissions of micro-pollutants such as heavy metals and dioxins remain a concern. Previous research on metal emissions has concentrated on overall mass balances, working either with laboratory or plant based measurements, or with computational models (frequently with little correlation between the techniques), leading to incomplete information on the system concerned. The waste incineration process is highly inhomogeneous, due to the changing nature of the waste feed, but the effects of changing waste feed and combustion conditions on the concentration and distribution of metals in incinerator residues has not been investigated fully until now. Therefore the main objective of this PhD research project was to develop a comprehensive understanding of metal behaviour during municipal solid waste incineration, including an assessment of the importance and effect of temporal variation in waste composition and incineration conditions, through a co-ordinated programme of experimental measurements and mathematical modelling. A new on-line continuous monitoring technique was developed in order to obtain temporally resolved data on metal concentrations in incinerator flue gases. This system was used to obtain unique data on the distribution of nineteen different metals in a UK municipal solid waste incinerator. It was found that not only was metal distribution highly dependent on the volatility of the metal concerned, but also that temporal fluctuations could be extremely significant. These were caused by changing waste feed and changing incinerator conditions. In parallel with the experimental programme, state-of-the-art thermodynamic modelling techniques were used to predict the distribution of metallic pollutants during waste incineration, for a range of waste compositions and combustion conditions. The thermodynamic equilibrium around various heterogeneous items in municipal waste was studied in order to a) assess the importance of non-uniformity in the waste stream, and b) investigate whether this could lead to the observed periodic changes in metal concentrations. These calculations, in conjunction with the experimental data obtained, have helped to show how unusual partitioning behaviour can be the result of local or transient behaviour on the burning bed, as well as changing bulk incinerator combustion conditions or bulk waste feed properties. These two approaches to the problem of understanding metal behaviour during municipal solid waste incineration have complemented each other extremely well. The presence of spikes in metal emissions has clearly been demonstrated, and probable causes have been identified. Heterogeneous items containing high proportions of volatile metal are the most likely source of the large spikes observed for some heavy metals, whilst other changes are linked to more general incinerator conditions. These results indicate that more careful sorting of municipal waste prior to incineration could significantly reduce the toxic metal spikes in the flue gas, and therefore the overall environmental impact of incineration, although the atmospheric emissions are already near-zero and are therefore of minimal impact.

The function of a flue-gas quench is to remove additional contaminants from flue-gas and to reduce the wastewater from a waste incineration plant. The aim of this degree project is to find how the system is affected by using a quench and what factors limits the performance. This is done by modelling and simulating a waste incineration plant in Aspen Plus. Data and plant schematics were obtained by a study visit to Mälarenergi Plant 6 situated in Västerås, Sweden, which were used as model input and for model validation. The results have shown that the amount of wastewater can be reduced by more than half compared to a plant without a quench. The heat produced in the condenser, when discharging water to the boiler, would be lowered by up to 20%. For systems with a quench present when more water was discharged to the boiler both the heat production and the pollutant capturing became better. However, the system has limits regarding the amount that could be recirculated, in the form of temperature limits in different parts of the system. In addition, if the heat load is low there is an insufficient amount of wastewater generated in the condenser to run the quench. In that situation, clean (fresh) water needs to be used instead. Using clean water is unwanted since the plant will then consume more resources while still producing less heat than a plant without a quench would.

Esta dissertação de mestrado tem como objetivo principal avaliar o transporte de poluentes de um lixiviado real de aterro sanitário em um solo laterítico do estado de São Paulo. A pesquisa objetiva também comparar dois métodos de avaliação de transporte de poluentes: ensaios laboratoriais e análise de dados de contaminação de campo. No aterro sanitário de Botucatu houve, comprovadamente, percolação do lixiviado pelo subsolo durante aproximadamente 15 anos, sob uma lagoa de acumulação de lixiviado sem revestimento de fundo. Foram coletadas amostras de solo subjacente à lagoa, uma areia argilosa, em três perfis verticais na superfície e nas profundidades de 0,25 m, 0,50 m, 1,00 m, 2,00 m e 4,00 m. Os poluentes investigados foram: arsênio, cádmio, carbono orgânico total (COT), chumbo, cloreto, cobre, cromo, ferro, manganês, níquel, nitrogênio Kjeldahl total (NKT) e zinco. Amostras indeformadas do solo local não contaminado foram também coletadas para ensaios de permeabilidade à água e ao lixiviado, assim como para ensaios de coluna. A condutividade hidráulica do solo é da ordem de 10-6 m/s, porém significativamente influenciada pelo gradiente hidráulico aplicado e pela duração da percolação. A condutividade hidráulica diminuiu com a percolação de lixiviado para ordens de grandeza entre 10-8 e 10-6 m/s, dependendo do gradiente hidráulico. Os ensaios de coluna mostraram concentrações efluentes dos elementos pesquisados superiores às afluentes, impossibilitando a obtenção de parâmetros de transporte de poluentes. A análise das amostras contaminadas coletadas in situ mostrou que, embora o solo local seja poroso e apresente alta permeabilidade, as concentrações dos elementos estudados eram inferiores aos limites legais de contaminação do órgão de controle ambiental estadual. O cloreto e o nitrogênio, para os quais não há limites legais, apresentaram-se no subsolo em concentrações elevadas, superiores às concentrações no solo natural e, em algumas amostras, às do lodo depositado no fundo da lagoa.
The aim of this research is to evaluate transport of pollutants from a sanitary landfill leachate through a Brazilian lateritic soil by two methods: laboratory tests and analysis of field contamination. In Botucatu Sanitary Landfill, leachate stored in an unlined pond infiltrated into the subsoil for 15 years. Samples of the subjacent soil, a porous clayey sand, were collected in three profiles located inside the area of the leachate pond at the following depths: surface, 0.25 m, 0.50 m, 1.00 m, 2.00 m and 4.00 m. The investigated pollutants were arsenic, cadmium, chloride, cooper, iron, lead, manganese, nickel, Kjeldahl nitrogen, total organic carbon (TOC) and zinc. The hydraulic conductivity measured in undisturbed and uncontaminated samples of the local soil, around 10-6 m/s, is significantly influenced by the applied hydraulic gradient and the percolation duration. When leachate substituted water as percolation fluid, the hydraulic conductivity decreased to values between 10-8 and 10-6 m/s depending on the hydraulic gradient. Chemical analysis of contaminated samples showed that concentrations of the researched elements in the subsoil were lower than legal maximum contamination limits established by the environmental agency of São Paulo state, in spite of the fact that the local soil is porous and has high hydraulic conductivity. On the other hand, chloride and Kjeldahl nitrogen, pollutants for which there are no legal limits, were found in concentrations much higher than background values, and in some samples even higher than those measured in the leachate sludge deposited in the bottom of the storage pond.

Thesis (Ph.D.)--Tufts University, 2000.
Submitted to the Dept. of Chemistry. Adviser: Albert Robbat, Jr. Includes bibliographical references. Access restricted to members of the Tufts University community. Also available via the World Wide Web;

Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (>450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration.
Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer.   Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (> 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.

This study investigates how different type of pollutants influence international firm performance. The dataset covers 1804 firms from 43 countries and 20 industries. Five different types of pollutants are used as well as five different financial performance measures. The paper uses industry-specific fixed effects as estimation method and finds that the type of pollutant influences the relationship between environmental performance and firm performance. In general, the relationship between pollutants and firm performance is negative, however water pollutants are an exception. Moreover, pollutants appear to be more negatively correlated with accounting performance measures than with market performance measures. Additionally, two country level factors show that the country of origin matters.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
FAPESP:00/00610-3

Hexachlorobenzene (HCB) is a pollutant, and there is an urgent need to degrade it. Two methods of degrading HCB to ethers are nucleophilic substitution and electroreduction, chosen for their viability and safety. The kinetics of substitution of HCB by potassium hydroxide and methanol were examined. The substitution of HCB by methoxide produced 1,2,3,5-tetrachloro-4.6-dimethoxybenzene (1,2,3,5-TCDMB) as the major substitution product, and side reactions produced extra chloride due to other substitution products. Thus, the proposed reaction mechanism is complicated due to the formation of ethers and phenols due to consecutive and parallel reactions. The substitution products of HCB were uncatalytically and catalytically electroreduced. Products with increasingly more methoxy substituents had lower electron affinities and increasing positive free energies. Catalysed electroreduction was more effective than uncatalysed electroreduction in dechlorinating the HCB substitution products to aromatic ethers. The most effective organic catalysts were those that possessed the lowest electron affinity as reflected in the reduction potential. A combination of nucleophilic substitution and electroreduction of HCB and its substitution products produced mono-, di- and trimethoxide chloroaromatic ethers and phenols. These products, particularly the ethers, may have future applications as fragrance ingredients
Doctor of Philosophy (PhD)

Naturally occurring plant derived phenols can be degraded through bacteria in swine waste. Chlorinated phenols, which are not naturally present in the environment, are toxic and generated from industrial activities as such petrochemical, pharmaceutical, plastic, rubber, pesticide, iron, steel, paper production, coal conversion, wood preserving, and cellulose bleaching. Large scale coal gasification and carbonization plants are another source of chlorinated phenols. Although not normally present in the environment, chlorinated phenols are structurally similar to many plant derived phenolics. It is our hypothesis that bacteria located in swine wastes may also have the ability to degrade chlorinated phenols. Identifying situations (and organisms) in which degradation of pollutants occurs is important field of research. Experimental work was focused on measuring the degradation of seven chlorinated phenols in swine waste using solid-phase micro-extraction (SPME) and gas chromatography(GC). Microbes in the waste perform respiration or fermentation to obtain the energy they need to carry out their life processes. Fermentation is a process in which electrons are transferred from one organic substrate to another and which results in incomplete degradation of organic compounds. Anaerobic respiration is a process in which organic substrates are degraded completely to CO2, but using substances other than oxygen as the terminal electron acceptor (such as Fe(III), NO3- or SO42-). Anaerobic respiration using these alternative electron acceptors provides an easier pathway for degradation of aromatics than fermentation alone. Usually the abundance of these electron acceptors in waste is low since microbes consume them readily and thus they must be added to the mixture. Our work focused on development of methods for the quantification of chlorinated phenols in swine wastes and results of bioremediation research. In this study, chlorophenols were extracted by SPME and analysed by GC. This research project mainly focused on the anaerobic degradation of chlorophenols in swine waste. It was observed that the decreased concentration of the chlorophenols was likely due to partitioning of the chlorophenols to solids, sticking to glass bottles and by bacteria present in the swine waste. In summary, it was observed that by ANOVA and gas production analysis 2,6-dichlorophenol and 2,4,5-trichlorophenol were likely to be degraded by bacteria present in swine waste.

The luxCDABE genes (i.e. full cassette) were inserted into the bacterial strain used in this study, E. coli HB101, using a multi copy plasmid, (pUCD607). A number of experiments were carried out in this thesis to study the potential of using the biosensor, E. coli HB101 (pUCD607), for ecotoxicity testing. Growth and bioluminescence of E. coli HB101 (pUCD607) were characterised and optimised, as well as the stability of this biosensor to a range of environmental parameters. The biosensors were found to be sensitive to a range of pollutants and provided a highly consistent bioluminescence response under conditions likely to be encountered in environmental toxicity testing. Assessment of the potential of the lux-based bioassay for revealing the combination of toxicities of metals was carried out. This is necessary because samples in ecotoxicity testing may contain a number of types of pollutants. The biosensors showed high sensitivity of response to mixed metals and identified the combined toxicity of the mixture. Biosensor bioluminescence could also be used to diagnose the distinction between toxicity after 15 and 30 minutes exposure. Results suggested that exposure time is an important factor affecting on the toxicity of metals in mixtures. The results from challenging lux-based biosensors with heavy metals with various concentration of Cl- demonstrated the effect of Cl- ion complex formation for metals on the bioluminescence of E. coli HB101 (pUCD607). The bioluminescence response of the biosensor also related to the results from computer modelling (GEOCHEM) and was used to diagnose the effect of Cl- on metal toxicity. The results showed that E. coli HB101 (pUCD607) is sensitive to complexes of metals such as are formed by Cl- ion. Immobilised cells of E. coli HB101 (pUCD607) were used to investigate the toxicity of metals, both singly and in mixture. This work aimed to assess the potential of immobilised cells, as an alternative form of biosensor, for use in ecotoxicity testing. Bioluminescence response of immobilised cells varied with the test solution pH and showed that it has great potential for use in low pH environments. Immobilised cell biosensors demonstrated sufficient sensitivity to identify the toxicity of individual and mixed metals. High levels of bioluminescence of immobilised cells lasted up to 5 hours after bead production, suggesting that biosensor immobilisation increases the flexibility of the toxicity assay.

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.

Biochars and hydrochars generated from organic waste streams such as forestry waste (Oak Wood), treated municipal waste, Digestate, Greenhouse waste (Paprika), Green waste and Pig manure have been characterized. In addition, model compounds; cellulose hemicellulose and lignin were also processed under identical conditions. Under standard conditions, the biochar yields ranged from 26% to 69% for biochar and 20% to 75% for hydrochar. Model compounds (lignin, cellulose and hemicellulose also had similar yields of 21% to 75%. Temperature was observed to have a great impact on biochar and hydrochar yields as they decrease with increasing temperature. Other process conditions such as time, doubling solid and additives such as acetic acid, 1%O2 and plastics also had similar impact on the yields of biochar and hydrochar. It also was observed that the biochemical components of the feedstock had no interaction, with each component decomposing separately. The fate and levels of macro nutrients, micro nutrients and heavy metals were also determined with most metals within the quality standards of the International biochar initiative and the European biochar certificate. Waste biochars were observed to have more nutrients when compared to woody biochars. Both nutrient and metal concentrations in the biochars and hydrochars were affected by the type of feedstock, processing technique and processing temperature with the elements increasing with increase in temperature, while some of the nutrients and metals were partitioned in the aqueous phase using hydrothermal carbonization technique. Acetic and formic acids used as additives extracted more metals into the aqueous phase, but the results are comparable to the metals extracted with water. Adsorbed organic hydrocarbons from the biochars and hydrochars were also determined. The Influence of processing conditions and feedstock composition on the nature and yields of extractable hydrocarbons, water extractable organic carbon (WEOC) and water extractable organic nitrogen is investigated. The nature of the hydrocarbons adsorbed onto the biochar and hydrochar has also been assessed using GC-MS, size exclusion chromatography and 1H NMR following exhaustive solvent extraction. Levels of polycyclic aromatic hydrocarbons (PAH) have been determined using single ion monitoring (SIM) from the extracted tars. Additional insight into the chemical and structural nature of the tars has been investigated using 1H NMR, FTIR and size exclusion chromatography. The levels of PAH adsorbed onto biochar are dependent upon feedstock and processing conditions. The levels of PAH ranged from 1.43 µg/g to 3.37 µg/g for hydrochars at 250°C, 1.63 µg/g to 9.79 µg/g for biochars at 400°C and 2.12 µg/g to 6.50 µg/g for biochars at 600°C respectively and were dependent on biomass, pyrolysis temperature, and time. With increasing pyrolysis time and temperature, PAH concentrations generally increase. Total concentrations were below existing environmental quality standards for PAH in soils. Total PAH concentrations in the hydrochars are comparable to biochars and fall between and fall within the quality standards. The levels of non PAH extractable hydrocarbons are higher at the lower temperature processing and include oxygenated hydrocarbons and nitrogen heterocycles although size exclusion chromatography suggests the majority of these tars have a high molecular weight. Hydrochars contain higher levels of tar compared to biochars. 1H NMR indicates the tars contain higher levels of aliphatic hydrogen in methyl or methylene groups. Thermal desorption GC-MS indicates that lower molecular weight hydrocarbons are also present adsorbed on both pyrolysis and HTC chars. This is not observed following solvent extraction due to loss on evaporation. Toxicity tests of the oak and municipal solid waste chars was observed not to have a toxic effect on a pure culture of Pseudomonas aeruginosa, a common microorganism in the soil.

In this study, the formation mechanisms, distribution characteristics, and potential environmental risks of hazardous air pollutants from industrial-scale waste incineration processes were investigated. First, to clarify the dominant formation mechanism of polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs) in a hazardous waste (HW) incinerator, three tests were designed by adding different precursors in phenol-containing raw materials. With the addition of p-dichlorobenzene, PCDD/F levels at the quenching tower outlet were ten times higher than levels observed at the inlet. This indicates that the quenching tower failed to suppress the formation of PCDD/Fs and surface-mediated precursor reaction is the dominant formation mechanism in low-temperature stages. Besides, adsoprtive memory effect in air pollution control devices (APCDs) also led to high PCDD/F emissions. These findings suggest that to control PCDD/F emissions, strict regulation of chlorine contents in feed materials and frequent cleaning of APCDs are necessary. Meanwhile, single particles and solid residues were collected from the same HW incinerator. Morphologies and elemental compositions of particles in flue gas and indoor air were characterized by transmission electron microscopy-energy dispersive X-ray spectrometry (TEM-EDS). Eight types of single particles were classified, as organic, soot, K-rich, S-rich, Na-rich, Fe-rich, mineral and fly ash particles. The heavy metal partitioning behavior study suggested that Hg, Cd and Pb were mainly enriched in fly ash through evaporation, condensation, and adsorption; while Cr, Cu, Mn, and Ni were mostly remained in the bottom ash due to their low volatilities. In addition, the study also investigated environmental behaviors of certain characteristic pollutants. Thrity-two soil samples surrounding a cement plant co- processing HW were collected and analyzed for the presence of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 heavy metals. Ten samples were selected for PCDD/Fs analysis. The highest concentration of PCDD/Fs occurred 1200 meters downwind from the cement plant. Levels of ∑16 PAHs ranged from 130.6 to 1134.3 μg/kg in soil. Source identification analysis suggested that the cement plant was the most likely source of PAH contamination. The concentrations of Cd and Hg were on average two times and six times higher than background values, respectively. Both incremental lifetime cancer risk model (ILCR) for PAHs and potential ecological risk index (RI) for heavy metals indicate potential risks to the population and the environment surrounding the cement plant. Last, to identify whether waste incineration is a major source for airborne environmentally persistent free radicals (EPFRs), tree leaf samples were collected from 120 sites surrounding four waste incinerators and one urban area. EPFR concentrations on leaves ranged from 7.5 × 10 16 to 4.5 × 10 19 spins/g. For the 10 N.D. samples, they were all collected from areas inaccessible by vehicles. Although previous work has linked atmospheric EPFRs to waste incineration, the evidence in this study suggests that vehicle emissions, especially from heavy-duty vehicles, are the main sources. According to our estimation, over 90% of the EPFRs deposited on tree leaves might be attributed to automotive exhaust emissions, as a synergistic effect of primary exhausts and degradation of aromatic compounds in road dust

Total organic carbon (TOC) and chemical oxygen demand (COD) are two methods used for measuring organic pollutants in wastewater. Both methods are widely used but the COD method results in production of hazardous wastes, including mercury.The purpose of this study was to validate the method TOC that will replace COD and find a factor to convert TOC to COD. In this study 26 samples were analyzed from four sewage treatment plant in the municipality of Enköping.The results show that the COD method could be replaced by the TOC method.The factor for COD/TOC was between 3.1 - 3.3. Both methods will be used in parallel until 2013 when it will be forbidden to use the COD analysis.

This project aims to investigate whether it is possible to detect consentrations down to 0,3 µg/L of oseltamirir in waste water by Quartz Crystal Microbalance. The risks linked to this contaminant could be not only environmental, scientists have found that infuence recistence can propagate due to contaminats of this kind. Cases similar to the bird- and swine-flu could occure if the drug spreads through animals and mutate.   Four systems of different character was synthesised. As a result it was found that MAA functional monomer systems probably was interfering with charges within it’s own nanowires. Reference systems could not detect 0,01 mg/mL and HEMA polymer surfaces was the only reliable system, pH of 5,1. Lowest limit of detection (LOD) was found in Molecular Imprinted Polymer nanowires (MIP Nw) at 0,01 mg/mL and could be scaled down to 0,1 mg/L with increased loop size (injection at 10x that of 0,01 mg/mL at about 500 µL and a halved flow rate.)   An alternative could be nano structuring such as ”polystyrene balls” that possibly could be able to achieve surfaces with even more binding sites needed to detect the lowest limit at 0,3 µg/L.

Dans un contexte de raréfaction de la ressource en eau, le traitement des eaux usées peut permettre de constituer des réserves d’eau durables et valorisables pour des usages variés tels que l’irrigation des cultures, la recharge de nappe phréatique ou encore une utilisation directe par les industries grandes consommatrices d’eau (cimenterie, aciéries…). Ainsi, la nécessité d’améliorer le traitement des eaux usées en sortie de STEU devient primordial afin d’assurer une qualité chimique et microbiologique de l’eau compatible avec sa réutilisation. Le traitement des micropolluants constitue notamment un nouveau défi pour les STEU. Si des projets de recyclage des eaux usées émergent pour les grandes STEU, le potentiel des petites ou moyennes STEU, qui constituent près de 90% des installations en France, reste inexploité à l’heure actuelle. Pour y remédier, les procédés d’oxydation avancée, notamment ceux basés sur l’UV, se présentent comme des solutions de traitement prometteuses. L’objectif de cette étude est de démontrer que la technologie UV/H2O2 est efficace et économiquement réaliste pour la désinfection et l’élimination des micropolluants organiques dans ces petites et moyennes STEU. Dans une première phase, un pilote de laboratoire UV/H2O2 a été évalué en conditions réelles (débit, matrice) sur des modèles bactériens et sur des micropolluants estrogéniques (E1, E2 et EE2) dans les eaux usées traitées d’une STEU. L’efficacité du traitement est comparée à celle de la photolyse seule. Il a été montré que le traitement UV/H2O2 permet une amélioration de la désinfection en assurant une destruction des bactéries contrairement à la photolyse seule qui ne fait qu’inactiver les micro-organismes. D’autre part, les doses UV (plus petit 600 mJ/cm²) et les concentrations en H2O2 étudiées (30-50 mg/L d’H2O2) permettent d’abattre plus de 80% de l’ensemble des micropolluants ciblés et de l’activité biologique (estrogénicité) associée, sans former de sous-produits estrogéniques ou toxiques au regard des tests d’activité employés dans l’étude (YES et Vibrio Fisheri). Parallèlement, il a été montré que le procédé UV/H2O2 est également efficace pour éliminer plus de 70% des produits pharmaceutiques (diclofénac, ibuprofène et naproxène) à 1000 mJ/cm². Sur la base des paramètres de traitement établis en pilote de laboratoire, un prototype a été dimensionné pour la STEU de Vercia (filtre planté de roseaux, 1100 EH, Jura). Les conditions de traitement mises en œuvre (dose UV plus pertit 1000 mJ/cm², [H2O2] = 15 mg/L) ont permis d’obtenir une eau de très haute qualité bactériologique et des abattements des micropolluants suivis supérieurs à 90%. Cette expérimentation à échelle réelle a permis d’estimer le coût global de cette technologie à environ 0,28 €/m³. L’ensemble de ce travail de recherche conclue à l’efficacité et au fort potentiel de la technologie UV/H2O2 pour le recyclage des eaux usées traitées des petites et moyennes STEU
Water scarcity is a growing concern worldwide. In this context, treated wastewater is seen as a sustainable water resource which could be used for different purposes such as irrigation, groundwater recharge or industrial activities. Reclaimed water is an environmentally and economically solution, still poorly developed in France. However, an increasing demand is expected in the coming years. Therefore, treatment enhancement in wastewater treatment plant could be necessary in order to meet chemical and biological water quality requirements which will depend on the final use of the treated water. The treatment of emerging micropollutants is one of the new challenge WTP will have to cope with. Enhanced treatment processes (ozonation, activated carbon, membrane filtration) have already been set up in large WTP but small and medium WTP, representing around 90% of the French WTP, are still lacking of affordable treatment solutions. However, UV based advanced oxidation process (AOP) could be a promising technology in order to produce a water of high quality. The aim of this study is to demonstrate that UV/H2O2 process is technically and economically efficient for the disinfection and the removal of micropollutants in small and medium WTP. First of all, a UV/H2O2 pilot at a laboratory scale was assessed on bacterial models as well as estrogenic micropollutants (E1, E2 and EE2) in treated wastewater. Treatment efficiency was compared to UV photolysis. It was shown that UV/H2O2 treatment increased the disinfection process by destroying the cellular membrane integrity whereas the UV photolysis could only inactive the bacteria. Moreover, when combining UV (plus petit 600 mJ/cm²) and H2O2 (30-50 mg/L), above 80% of the estrogenic compounds and the associated estrogenic activity could be removed. No high estrogenic or toxic by-products were detected by the two bioassays used in this study (YES and vibrio fisheri). The UV/H2O2 process could also degrade pharmaceuticals such as diclofenac, ibuprofen and naproxen (>70 % at 1000 mJ/cm²). In a second part, a full scale pilot was designed based on the previous results and set up in a WTP in Vercia (Jura). The treatment (UV fluence ≈ 1000 mJ/cm², [H2O2] = 15 mg/L) allowed to obtain a water of a very high bacteriological and chemical quality. The global cost of the process was estimated at around 0.28 €/m³. This study demonstrates the efficiency of the UV/H2O2 process in a small WTP and its high potential for reclaimed water production

This dissertation explores a combined adsorption and advanced oxidation technology for trapping and destruction of organic pollutants in waste water. The adsorbed/immobilized pollutant onto the surface of metal supported catalyst is oxidized via advanced oxidation technology. The advanced oxidation process is carried out using Co[superscript]2+/KHSO[subscript]5 (Cobalt/peroxymonosulphate) reagent to generate highly active sulphate radical (SO[subscript]4*), which can readily attack and oxidize the organic pollutants in waste water. The reaction mechanism of Co[superscript]2+/KHSO[subscript]5 reagent follows similarly to the Fenton reagent (Fe[superscript]2+/H[subscript]2O[subscript]2) which is used to generate hydroxyl radical (OH*). Co[superscript]2+/KHSO[subscript]5 reagent has been successfully utilized for bleaching applications and oxidation of organic contaminants. Compared to hydroxyl radical, the sulphate radical is highly potent to oxidize contaminants even at basic pH. However the biggest disadvantage of using Co[superscript]2+/KHSO[subscript]5 reagent is the dissolution of Co[superscript]2+ ion into the water which poses a severe environmental hazard. In the current study, cobalt ion is incorporated into supporting media and utilized for advanced oxidation.Very few studies have so far explored the heterogeneous oxidation technology based on Co[superscript]2+/KHSO[subscript]5 for the treatment of organic contaminants in water. With this research focus, various support media have been utilized to load cobalt ions, which included Zeolite A, Zeolite X, ZSM-5, SBA-15, Silica and Activated Carbon. Cobalt metal was incorporated into commercial Zeolites by ion exchange technique whereas in-situ cobalt loading was carried out during the synthesis of SBA-15. Cobalt loading was done into Silica and Activated Carbon by conventional impregnation technique. The choice of cobalt loading technique inherently determines the oxidation state of cobalt species loaded into the sample which in turn determines the oxidation efficiency. Furthermore, the choice of cobalt precursor significantly affects the metal-support bonding which has been investigated by loading on silica support with different types of cobalt precursor such as cobalt chloride, cobalt acetate and cobalt nitrate. Many of these supports such as Zeolite ZSM-5 and Activated Carbon have never been tested before for cobalt loading and oxidation via sulphate based oxidant and demonstrate efficient oxidation of phenolic pollutants.The investigation of organic oxidation using sulphate based oxidants was further extended into photocatalytic reactions. Photo degradation was carried out using artificial solar light and germicidal UV radiation in the presence of ZnO and oxidants such as peroxymonosulphate, peroxidisulphate and hydrogen peroxide. The comparison of photochemical and photocatalytic oxidation was carried out and their synergy of combination was explored.The thesis provides a thorough exploration of heterogeneous oxidation via sulphate based oxidant for the treatment of organic pollutants. The supported catalysts investigated here can be further improved and utilized as a PRB media for groundwater remediation. A final chapter discusses about the mathematical modeling of a column test to mimic a lab scale PRB in order to investigate the process parameters affecting the PRB design. The column modeling also directs towards a development of a novel “Reactive Adsorber” for the treatment of industrial waste by combined adsorption and oxidation.

Se utilizan diferentes procesos para el tratamiento de las aguas residuales. Sin embargo, estas tecnologías son ineficaces, generan productos secundarios o son demasiado caras. El objetivo principal de esta tesis es la eliminación de diversos contaminantes del agua, incluyendo metales, tintes y productos farmacéuticos mediante dos tecnologías. La primera consiste en un tratamiento físico-químico de adsorción sobre carbón activo preparado a partir de un resido de la industria agroalimentaria. El segundo se trata de un tratamiento biológico con hongos. En cuanto a la adsorción sobre carbón activo, en una primera etapa se consideran aspectos tales como la preparación del adsorbente, su caracterización y el estudio del impacto ambiental asociado a su producción. Para la preparación de carbón activo se realiza la activación química a partir de orujo de oliva, utilizando ácido fosfórico como agente deshidratante. Se varían los parámetros principales del proceso para optimizar las condiciones de la activación. El carbón activo preparado, se caracteriza teniendo en cuenta sus propiedades de adsorción, su estructura química y su morfología. Los resultados muestran que el adsorbente más eficaz es el que se obtiene bajo las siguientes condiciones: una concentración igual a 60% de H3PO4, una relación de impregnación de 1,75, y una temperatura de pirolisis de 450°C. El adsorbente preparado en estas condiciones presenta buenas características en comparación con los que se encuentran en la literatura. Para minimizar el impacto ambiental, ciertas modificaciones podrían incorporarse en el proceso de preparación del adsorbente tales como la recuperación del gas derivado de la etapa de pirolisis y su utilización como fuente de energía, y la recuperación de ácido fosfórico después de lavar el carbón activado. Después de establecer las condiciones óptimas se evalúa la eficiencia del carbón activo para la eliminación de los contaminantes inorgánicos y orgánicos. Para los metales, cogiendo Cu2 + como un modelo, los ensayos de adsorción en columna muestran la alta capacidad del carbón activo para reducir KMnO4 en óxido insoluble de manganeso (MnO2) que impregna la superficie del adsorbente, cuya presencia mejora significativamente los resultados de la adsorción de Cu2+ sobre el carbón activo. En cuanto a los contaminantes orgánicos, el estudio muestra la eficacia del carbón activado para eliminar colorantes de los efluentes sintéticos y reales y productos farmacéuticos de soluciones de compuestos puros y formando parte de una mezcla de fármacos. En la mayoría de los casos los modelos de Langmuir y pseudo-primero orden presentan el mejor ajuste para la isoterma y la cinética, respectivamente. La temperatura afecta la adsorción de colorantes, sin embargo, la variación de pH no tiene ninguna influencia. Al contrario que en la adsorción de los fármacos. En cuanto al proceso biológico adaptado, se ha comprobado el potencial de tres hongos ligninolíticos (Trametes versicolor, Ganoderma lucidum y Irpex lacteus) para la decoloración de un colorante de la industria de curtidos. Los resultados indican que Trametes versicolor es la mejor cepa tanto en términos de extensión y rapidez en la decoloración. Tanto en procesos en discontinuo como en discontinuos repetidos en un reactor fluidizado por pulsos de aire y con reuso de biomasa muestra que la capacidad de decoloración del hongo es del 86-89% y no disminuye durante los discontinuos repetidos a pesar de la baja actividad enzimática detectada. Se ha evidenciado que la lacasa es una enzima involucrada en la biodegradación y que el fenómeno de adsorción que ocurre en la biomasa fúngica. Finalmente, la combinación del tratamiento mediante hongos y la adsorción en adsorbentes de bajo coste puede ser una estrategia adecuada para depurar efluentes complejos.
Different processes are used for the treatment of wastewaters. However, they are either frequently ineffective, or they generate secondary products or worse, they are too expensive. The main objective of this dissertation is the removal of various contaminants in water including metals, dyes and pharmaceuticals products via two environmentally- friendly technologies. The first consists in a physico-chemical treatment- by adsorption on activated carbon prepared from olive-waste cakes. The second is about a biological treatment using white-rot fungi. First, the adsorbent preparation, its characterization and the study of the environmental impact associated with its production are considered. Chemical activation of the feedstock olive-waste cakes, using phosphoric acid as dehydrating agent, is adopted for activated carbon preparation and main process parameters (such as acid concentration, impregnation ratio, temperature of pyrolysis step) are varied to optimize the best conditions. The activated carbon prepared under the optimal conditions is then fully characterized considering its adsorption properties as well as its chemical structure and morphology. The results show that the most efficient adsorbent is that obtained under the following optimal conditions: an acid concentration equal to 60% H3PO4, an impregnation ratio of 1.75, and a pyrolysis temperature of 450 °C. The adsorption characteristics of the adsorbent prepared under such conditions presents good characteristics compared with the previous reports for activated carbon in the literature. To minimize the environmental impact, certain modifications could be incorporated in the process of adsorbent preparation such as recovery of the gas derived from the pyrolysis step, its reuse as an energy source, and the recovery of phosphoric acid after activated carbon washing. After establishing the optimal conditions, the efficiency of the optimal activated carbon for the removal of inorganic and organic pollutants is then evaluated. For heavy metals, considering the adsorption of Cu2+ ions as a model, column adsorption tests show the high capacity of the activated carbon to reduce KMnO4 into insoluble manganese (IV) oxide (MnO2) which impregnated the sorbent surface. The results also indicate that the adsorption of Cu2+ can be significantly improved by the presence of MnO2 fixed on activated carbon. Concerning the organic pollutants, the study shows the effectiveness of the activated carbon to remove dyes from individual and real effluents and pharmaceutical products from single and mixture solutions. Many models are used to understand the adsorption behavior and in the most cases Langmuir and pseudo-second order models present the best fit for the isotherm and kinetics, respectively. Temperature is found to affect the adsorption of dyes, however, the pH variation has no influence. The opposite case is found for drugs adsorption. Regarding the biological process adapted, the potential of three white-rot fungi (WRF) (Trametes versicolor, Ganoderma lucidum and Irpex lacteus) to decolorize the commercial tannery dye − Black Dycem – is investigated in solid and liquid media. The results indicate that Trametes versicolor is the best strain both in terms of extent and rapidity of decolorization. The experiment, performed in single and repeated batches in an air-pulsed bioreactor with biomass reuse of the fungus Trametes versicolor, shows that the decolorization capability of the fungus does not decrease during the repeated batches and the fungus is able to remove 86−89% of the dye despite the low enzyme activity detected. The results also show that the biodegradation mechanism plays a noticeable role in the decolorization process of the dye by means of laccase activity in addition to the adsorption phenomenon occurring on the fungal surface. Finally a combination of fungal treatment and adsorption on low cost adsorbents could be a suitable strategy to remove pollutants from complex effluents.

A methodology based on an analytical protocol for evaluation of hazards from landfill leachate and solid waste is described. A dynamic analytical protocol, the LAQUA protocol, including measurements of inorganic and water-quality parameters, polar and non-polar organic marker compounds, and toxicity, was constructed. An acute toxicity test, using the brackish water crustacean Artemia salina as test organism, was developed. The methodology was applied to authentic problems such as investigation of different treatment techniques for landfill leachate, evaluation of leaching tests and characterization of solid wastes, and an investigation of a filter material aimed for leachate treatment. Investigated treatment methods comprised in all cases pre-treatment by aeration combined with sedimentation, followed by one of: bioremediation, ozonation, chemical oxidation by Fenton’s reagent, or geo-bed filters. Evaluated filter materials were mixtures of natural or residual waste products. A combination of pre-treatment followed by a geo-bed filter containing a mixture of peat and carbon-containing ash gave an efficient simultaneous removal of metals and organic pollutants. The performance of two leaching tests for characterization of solid waste, the up-flow percolation test (SIS-CEN/TS 14405:2004) and the batch test (SS-EN 12457 -3), was investigated. Solid waste materials (sludge from street gutters and fragmented metallic waste) were characterized using leaching tests and the hazards of the materials were evaluated in the eluate, obtained at specific liquid-to-solid ratios (L/S). The L/S 2 and L/S 10 values were compared with limit values included in the waste acceptance criteria (WAC). The analyses were extended towards specific organic compounds, such as individual phenolic compounds and polychlorinated biphenyls (PCB). Organic compounds were found in eluates from both types of tests, showing the possibility to use these methods to evaluate the leaching of such compounds from waste materials. The use of authentic leachate as leachant, leads to increased concentrations of heavy metals in the eluate, compared to the prescribed use of demineralised water as leachant. Generally good agreement was found between the results of the two leaching methods. A strategy based on batch tests is described for investigation of a filter material for leachate treatment. Batch tests gave suitable information about the leaching from new and used material, and showed high removal efficiencies of metals and non-polar organic compounds. However, for investigation of removal of polar organic markers (e.g. phenolic compounds) a batch test is not sufficient and should be supplemented by a column test.
Avfall har alltid uppkommit i alla samhällen i alla tider. Det vanligaste sättet att hand om det har varit att samla avfallet i soptippar (deponier) på mark som ansetts obrukbar, t.ex. i sankmarker utanför bebyggelsen. I takt med ökad konsumtion och produktion har också mängderna avfall ökat. Anledningen till att avfall och avfallshantering kommit alltmer i fokus i miljödebatter under de senaste decennierna, är inte bara de stora mängderna avfall på de många och stora sopbergen runt om i världen. Deponierna släpper också ifrån sig miljöfarliga ämnen från de alltmer komplexa produkter som blivit lagda i deponin. Dessa kommer att fortsätta att läcka ut länge efter det att deponeringen på soptippen slutat, och skapa problem för människor och miljö i flera generationer. Som en konsekvens av internationella beslut bl.a. Agenda 21 (FNs miljökonferens i Rio) och EUs lagstiftning om avfallshantering som Sverige har tagit in i sin lagstiftning, kommer bl.a. antalet soptippar att minska. Efter den 31 december 2008 beräknas endast ett 90-tal deponier för kommunalt avfall att vara i drift i Sverige. Lagstiftningen beskriver en avfalls hierarki där deponering är den sämsta och absolut sista åtgärden som får göras bara när inget av de andra alternativen kan uppfyllas. Det ställs stora krav på de soptippar som är godkända enligt den nuvarande lagstiftningen. Olika typer av deponier ska finnas för olika slag av avfall. En deponi för farligt avfall har bättre skydd mot läckage både under och över tippen än en tipp för icke-farligt avfall. För att ha kontroll på vilket avfall som läggs på deponin och därmed kunna behandla det på korrekt sätt, måste avfallet beskrivas och klassas innan det skickas för deponering. Karakteriseringen görs bl.a. med hjälp av lakningstester. Syftet med denna avhandling har varit att utarbeta en metodik för at utvärdera miljöfarliga ämnen som kommer från avfall och lakvatten från soptippar. Den inledande forskningen utgjordes av ett projekt kallat Laqua, finansierat av EU-kommissionens program för samarbete inom Östersjöregionen, SweBaltcop. Projektets uppgift var att främja utveckling av ekologiskt och ekonomiskt hållbara reningsmetoder för lakvatten. Lakvattnet bildas främst av nederbörd som faller över deponin. Det vatten som kommer in i soptippen tar med sig många av de ämnen som finns i tippen när det rinner ut. Dessa ämnen kan komma från sådant som har deponerats eller bildas när avfallet bryts ner. Lakvattnet samlas upp och renas på något sätt innan det släpps ut till ett naturligt vattendrag. En vanlig metod att behandla lakvatten är att pumpa det till det kommunala avloppsreningsverket och rena det tillsammans med avloppsvatten. Men detta är ingen optimal lösning eftersom lakvatten innehåller andra föroreningar än avloppsvatten, t ex salter, tungmetaller och svårnedbrytbara organiska föreningar. Avloppsreningsverken är konstruerade för att rena avloppsvatten och lakvattnets föroreningar kan störa reningsprocessen. Framför allt kan de känsliga mikroorganismerna i det biologiska reningssteget påverkas negativt. Slammet som bildas vid reningsprocessen kommer att koncentrera många av de oönskade föroreningarna som härstammar från deponin. Slammet är egentligen ett utmärkt gödselmedel för jordbruket, men på grund av att slammet är förorenat av tungmetaller och svårnedbrytbara organiska ämnen kan inte slammet användas. Slammet blir då ett avfall som kommunen inte kan bli av med utan stora kostnader. Många kommuner har därför valt en separat rening av lakvattnet. Val av reningsteknik är beroende av flera faktorer, som volymerna lakvatten som uppkommer, innehållet av de olika miljöfarliga ämnena, vart det renande vattnet ska släppas ut och utrymme för att bygga en reningsanläggning. För att utvärdera olika tekniker för rening av lakvatten, byggdes en försöksanläggning på soptippen i Kristianstad. För att kunna utvärdera en reningsmetod måste bestämningar av koncentrationer av olika ämnen (analyser) göras. På grund av den ökande oron för organiska miljögifter som PCB och fenoler, skulle reningsteknikerna utvärderas med fokus sådana eller liknande ämnen. Analyser av organiska ämnen är komplicerade och tidskrävande, och det är inte möjligt att analysera alla ämnen. I många undersökningar används endast generella parametrar för att uppskatta innehållet av organiska ämnen, men dessa metoder ger ofta inte tillräcklig information om det egentliga innehållet i lakvattnet. Därför utarbetades ett utvärderings protokoll, LAQUA protokollet (artikel I) för bestämning av organiska miljögifter i olika förorenade vatten. Detta protokoll innehåller förutom analyser för organiska miljögifter som PCB och fenoler och en akut toxicitetstest, även standardiserade rutinanalyser av metaller och vattenkemiska parametrar. Eftersom separat analys av alla organiska ämnen inte nödvändig för att bedöma olika reningsmetoder för lakvatten, innehåller protokollet ett antal markörer för polära, respektive opolära organiska föreningar. Den biologiska giftighetstesten som utvecklades (artikel III) och ingår i protokollet är ett s.k. akut toxicitetstest, dvs. organismen påverkas direkt av höga halter av föroreningar. I testen används det lilla saltvattentåliga kräftdjuret Artemia salina, som säljs som föda åt akvariefiskar. En bestämd volym med ett antal Artemia larver läggs i små brunnar med olika koncentrationer av lakvatten under 24 timmar. Sedan jämförs vid vilken inblandning av lakvatten som hälften av kräftdjuren har fått rörelsestörningar. Resultaten på tester med obehandlat lakvatten, respektive behandlat med olika reningstekniker jämförs, och på det viset kan effektiviteten på reningsmetoder bedömas gentemot en vattenlevande organism. Utvärderingen av försöksanläggningen (artikel II) visade att vid förbehandlingen, bestående av luftning och sedimentering, togs mycket av föroreningarna bort, och det rekommenderas att ett sådan reningssteg alltid bör finnas vid en reningsanläggning för lakvatten. De kemiska behandlingsmetoderna med ozon och Fentons reagens (tvåvärt järn och väteperoxid) var effektiva på att ta bort de organiska miljögifterna, men även de mer kostnadseffektiva filterbäddarna visade sig fungera bra. Den goda erfarenheten från försöksanläggningen av filterbäddar ledde till att effektiviteten hos fler filter material undersöktes. I artikel VI beskrivs ett försök, gjord i laboratorium, där lakvatten från en soptipp som tar hand om industri avfall (metallavfall från bl.a. bilar och kylskåp) fick rinna genom kolonner med olika filtermaterial. Mixen av torv och aska med kolinnehåll visade sig vara bra på att ta bort både metaller och organiska ämnen från lakvattnet. Kunskapen från bl.a. dessa undersökningar har bidragit till att en fullskaleanläggning för lokal rening av lakvatten har kunnat byggas i anslutning till Stena metalls soptipp i Halmstad. Den andra delen i avhandlingsarbetet riktade in sig mot lakningstester. För att undersöka vilka ämnen som kan lakas ut från ett avfall rekommenderas två olika standardiserade lakningstests metoder. Vid den ena metoden pumpas en vätska genom en kolonn med en uppvägd mängd avfall tills ett visst vätske/fast fas förhållande (L/S halt) har uppnåtts. Vid den andra snabbare metoden, skakas en bestämd mängd avfall tillsammans med en bestämd volym vätska under 24 timmar. Den vätska som man får efter testerna kan jämföras med ett lakvatten och ska simulera den urlakning som avfallet ger ifrån sig under sin tid på deponin. Denna urlakningsvätska analyseras och de uppmätta halterna av olika ämnen jämförs med en gränsvärdes tabell och avfallet kan hänföras till en avfalls klass. De två lakningstesterna användes för att karakterisera olika avfallsslag, sönderdelat metall skrot (artikel IV) och slam från gatubrunnar (artikel V). För att få mer kunskap om metoderna och kunna vidareutveckla dem, utökades undersökningarna och analyserna. De urlakade vätskorna analyserades därför enligt Laqua protokollet, dvs med markörer för organiska miljögifter. Dessutom gjordes undersökningar där lakvatten användes som lakningsvätska istället för avjonat vatten som testmetoderna föreskriver. Dessa visade att den mer jonstarka vätskan (lakvattnet) ökade urlakningen av metaller från avfallet. En jämförelse av de två metoderna visade att den snabbare skaktesten oftast gav likvärdiga eller högre halter av de analyserade ämnena i urlakningsvätskan, och därmed kan den i många fall användas i första hand. För att bedöma ett filtermaterial ur ett livstidsperspektiv, utvecklades en strategi baserad på skaktester (artikel VII). Ett filtermaterial, en mix av torv och aska med kolinnehåll, undersökes före och efter att det använts i en filterbädd för rening av lakvatten. För att vara säker på att filtermaterialet i sig själv inte släppte ifrån sig några föroreningar gjordes en lakningstest. För att se hur effektivt materialet var på att ta bort metaller, PCB och fenolföreningar, gjordes skaktester med vätskor med kända halter av dessa föroreningar. När filtermaterialet är förbrukat och skall bytas ut anses det som ett avfall, och det karakteriserades med lakningstest för att hur det skulle tas om hand. Metodiken med skaktester ger bra information om utlakning från ett material, och skaktester är också bra instrument för att utvärdera ett filtermaterials effektivitet på att ta hand om metaller och opolära organiska ämnen som PCB. Men för att utvärdera effektiviteten av borttagandet av polära organiska ämnen (t ex. fenoler), är inte en korttids skak test något bra instrument. Reduceringen av dessa ämnen sker genom nedbrytning med hjälp av mikroorganismer, och för att undersöka detta behövs tester som varar en så lång tid att en mikrobiologisk miljö hinner etablera sig, t ex. kolonn tester. Utvärderingen av detta avhandlingsarbete visar på några ytterligare slutsatser och förslag till fortsatt arbete. Toxicitetstesten med Artemia bör kompletteras med tester på t ex. bakterier och växter, eftersom det inte räcker med en test på bara en organism för att bedöma giftigheten av en förorening ett naturligt ekosystem. Vidare behövs en biologisk test för att påvisa kroniska effekter, så som skador på fortplantning eller tumörsjukdomar. Dessa skador kan uppkomma genom att organismer påverkas under en lång tid av de låga, men därmed inte ofarliga halter av organiska miljögifter som ofta förekommer i lakvatten. Den presenterade metodiken kan användas för att utvärdera miljöfarliga ämnen från olika förorenade områden. Avhandlingen har visat att LAQUA protokollets sammansättning och dess analyser är ett bra instrument för att utvärdera reningstekniker för lakvatten och för att ge ytterligare information om organiska ämnen i fast avfall. Bedömning av luft kvalitet och karakterisering av dagvatten är andra exempel där metodiken kan användas. Avslutningsvis är det förstås lättare att utvärdera farligheten från avfall när det är mindre volymer avfall att utvärdera. Detta kan uppnås genom att konsumera mindre, återanvända produkter, återvinna material, utvinna energi ur avfallet och välja miljövänliga produkter när man köper nytt.

Orientador: Li Li Min
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Ciências Médicas
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Resumo: Embora o avanço tecnológico tenha viabilizado o uso dos sistemas digitais para a aquisição de imagens radiográficas, ainda hoje, no Brasil, os filmes radiográficos convencionais continuam sendo os tipos de receptores mais utilizados nos consultórios odontológicos. Deste modo, após a exposição aos raios X, os filmes radiográficos devem ser processados em soluções químicas a fim de que a imagem latente seja convertida em imagem real, passível de análise para diagnóstico. Sabe-se que, tanto o revelador quanto o fixador radiográfico contém em sua composição substâncias químicas altamente tóxicas, podendo apresentar risco à saúde de profissionais, que podem desenvolver lesões cutâneas e dermatites em decorrência do manuseio e manipulação destas soluções de processamento, além de apresentarem risco à saúde pública, caso ocorra a ingestão de produtos oriundos do meio ambiente previamente contaminado e ainda, sérios prejuízos ao meio ambiente, contaminação da fauna e flora, em virtude do descarte indevido destas soluções após seu uso. Tendo isto em vista, os objetivos deste trabalho foram: 1) Avaliar a eficácia de um novo modelo de recipiente para processamento radiográfico manual em câmara-escura portátil, para uso em consultórios odontológicos; 2) Avaliar qualitativamente e quantitativamente as imagens radiográficas obtidas por meio do processamento radiográfico nos diferentes recipientes; 3) Comparar os resultados obtidos em ambas as análises; sob a hipótese de que, devido às suas configurações geométricas, este novo modelo de recipiente propiciaria a economia de soluções químicas para que a execução do processamento radiográfico manual, reduziria os custos aos profissionais da área odontológica e, além disto, promoveria a redução do impacto ambiental devido à minimização da quantidade de químicos usados nestes recipientes. Para atender aos objetivos e conhecer sobre a aplicabilidade deste trabalho, realizou-se um outro estudo no qual se fez uma investigação sobre o descarte dos Resíduos de Serviço de Saúde produzidos em consultórios odontológicos localizados no Estado do Tocantins, Brasil. O estudo abordou aspectos relacionados ao conhecimento e atitudes dos cirurgiões dentistas frente aos resíduos gerados em seu ambiente de trabalho, e sua percepção sobre os resíduos gerados nos demais consultórios odontológicos. Um questionário foi aplicado a 239 cirurgiões-dentistas. Destes, 78,2% trabalhavam em clínica particular e 68,6% já haviam cursado alguma pós-graduação. Do total dos entrevistados, 87,9% afirmaram realizar exames radiográficos em seu consultório e estes foram unânimes em afirmar que o processamento das imagens era realizado manualmente em câmara-escura portátil e a maioria dos entrevistados (88,1%) afirmou que, em média, a cada 5 dias, descartava no esgoto as soluções químicas de processamento utilizadas. Ademais, 30,1% dos participantes acreditavam que os resíduos de amálgama eram descartados, por outros profissionais, em lixo comum e outros 8,8% supunham que o descarte era feito na pia dos consultórios; 61,9% acreditavam que o lixo contaminado (infectante) era disposto juntamente com o lixo comum e, em relação os resíduos perfurocortantes, 14,2% acreditavam que eram descartados em recipientes plásticos e 9,2% em lixo comum. Por meio deste trabalho, concluiu-se, que, em geral, os cirurgiões-dentistas entrevistados desconheciam sobre o correto descarte dos resíduos de serviço de saúde, uma vez que foi observada negligência desta prática por muitos deles, além da percepção de que outros profissionais também realizavam o descarte incorreto dos resíduos gerados em seu ambiente de trabalho. De posse destas informações, testou-se um novo modelo de recipiente para processamento radiográfico manual. Foram obtidas imagens radiográficas dos dentes posteriores de um phantom de mandíbula humana macerada e em seguida, estas imagens foram processadas em quatro câmaras-escuras portáteis. Em uma delas foram colocados dois recipientes convencionais (R1) abastecidos com 200ml das soluções de processamento e, em cada uma das demais câmaras-escuras, para este mesmo propósito, foi disposto um par de cada um dos três tipos de recipientes desenvolvidos pelos autores, R2, R3 e R4, abastecidos com 12, 19,2 e 24ml das soluções reveladora e fixadora respectivamente. Foram processadas 184 películas em R1, 40 em R2, 48 em R3 e 56 em R4. As películas radiográficas foram digitalizadas e posteriormente submetidas à análise objetiva no programa MaZda; em seguida, foram dispostas de maneira ordenadas, obedecendo a sequência do processamento, em papel cartão preto, para que pudessem ser submetidas à análise subjetiva. Os resultados da análise subjetiva mostraram que houve concordância dentre os cinco examinadores em relação às imagens consideradas aceitáveis para diagnóstico para os quatro recipientes estudados, e os resultados da análise objetiva mostraram que as imagens foram consideradas satisfatórias para diagnóstico até o 15º dia de pesquisa para R1, até o 4º dia para R2 e R3, e 5º dia para R4. A análise subjetiva mostrou-se menos sensível que a objetiva na avaliação da qualidade das imagens radiográficas processadas nos recipientes convencionais (R1), porém, mostrou grande correlação com a objetiva na avaliação da qualidade das imagens processadas nos demais recipientes (R2, R3 e R4). Deste modo, concluiu-se que o novo modelo de recipiente viabilizou o processamento de películas radiográficas em câmara-escura portátil, utilizando menor quantidade de soluções químicas para o processamento radiográfico manual, sendo que estas se apresentaram com qualidade satisfatória para diagnóstico.
Abstract: Even though the technological advances have allowed the utilization of digital systems for acquisition of radiographic images, conventional radiographic films are still the most used in dental offices in Brazil. Thus, after X-ray exposure, the radiographic films must be processed in chemical solutions to change the latent stored images into visible images for diagnostic purposes. Both the developer and fixer contain highly toxic chemical substances that may endanger the health of professionals, who may present skin lesions and dermatitis due to handling of these solutions. These chemicals may also constitute a public health problem if contaminated products of the environment are ingested, besides posing serious risks to the environment by contamination of the fauna and flora if these chemical solutions are improperly discarded after utilization. Therefore, this study aimed to: 1) evaluate the efficacy of a new container for manual radiographic processing in portable darkrooms for utilization in dental offices; 2) qualitatively and quantitatively evaluate the radiographic images obtained by radiographic processing in the different containers; 3) compare the results obtained in both analyses, considering that the design of the new container would allow dental professionals to save the chemical solutions used for manual radiographic processing, reducing the costs and also the environmental impact, considering the minimization of the quantity of chemical solutions used in these containers. To meet these objectives and know the applicability of this study, a previous study was conducted in which we investigated the discard of Health Service Wastes produced in dental offices of the state of Tocantins, Brazil. The study discussed the aspects related to the knowledge, perception and attitudes of dentists towards the waste generated in their work environment. We interviewed 239 dentists using a structured questionnaire, of whom 78.2% worked at private offices and 68.6% had post-graduate degree. From the total of respondents, 87.9% stated that they did perform intraoral radiographic exams in their offices, and these professionals unanimously used portable dark rooms from commercial brands for radiographic processing. Most dentists (88.1%) that perform radiographic exams in their offices declared that the mean period for changing the radiographic processing chemicals was 5 days. Conversely, 30.1% of participants believed that amalgam wastes were discarded in common garbage, and 8.8% believed that amalgam wastes were discarded in the offices' sink; 61.9% of them believed that the infectious waste were discarded together with the common garbage. Regarding the sharp objects, 14.2% believed that these were discard in plastic recipients, and 9.2% believed that the majority of dentists discarded sharp objects in the common garbage. The data obtained in this study revealed that, in general, the dentists interviewed were unaware of the correct procedures for the discard of health service waste, since there was both negligence in these practices by many of them and the perception that other professionals also performed incorrect discard of waste generated in their work environment. After achievement of these data, a new model of container for manual radiographic processing was tested. Radiographic images were obtained from the posterior teeth of a phantom dry human mandible and processed in four portable darkrooms. One darkroom had two conventional containers (R1) filled with 200ml of processing solutions. For the same purpose, each of the other darkrooms had one pair of the three types of containers designed by the authors, namely R2, R3 and R4, filled with 12, 19.2 and 24ml of developing and fixer solutions. A total of 184 films were processed in R1, 40 in R2, 48 in R3 and 56 in R4. The films were digitized and objectively analyzed using the software MaZda; following, they were arranged according to the sequence of processing in black cardboards for subjective analysis. The results of the subjective analysis revealed good agreement between the five examiners concerning the images considered acceptable for diagnosis for all four containers investigated. The results of the objective analysis demonstrated that the images were considered satisfactory for diagnosis until the 15th day of investigation for R1, fourth day for R2 and R3, and fifth day for R4. The subjective analysis was less sensitive than the objective analysis to evaluate the quality of radiographic images processed in the conventional containers (R1), yet presented high correlation with the objective analysis for evaluation of the quality of images processed in the other containers (R2, R3 and R4). Thus, it was concluded that the new model of container allowed processing of radiographic films in portable darkrooms using a smaller quantity of chemical solutions for manual radiographic processing and presenting satisfactory quality for diagnosis.
Doutorado
Neurocirugia
Doutor em Fisiopatologia Medica

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Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Conventional waste water treatment processes are not completely effective in removing highly stable organic compounds. Photocatalytic degradation on titanium dioxide is a possible alternative technique for many classes of these compounds. Several studies have been done by other researchers to study mechanisms of photocatalytic degradation, which occurs either through direct oxidation by holes or via indirect oxidation by radical messengers. Titanium dioxide can oxidize substrates directly through hole oxidation mechanisms or indirectly through free radical mechanisms. Substrates must bind onto the catalyst surface to undergo direct oxidation by holes. Thermogravimetric analysis (TGA) was performed on four different classes of compounds; iodinated contrast agents (iohexol and diatrizoate), polycyclic aromatic hydrocarbons (perylene and pyrene), the antibacterial agent triclosan and the pesticide atrazine, to investigate which of the compounds are adsorbed on the surface of titanium dioxide to undergo direct oxidation through electron holes. Differential scanning calorimetry (DSC) was conducted on triclosan and atrazine to determine if the desorption reaction is endothermic or exothermic. Powder X-ray diffraction was performed on all four classes of compounds to observe diffraction pattern of these compounds.

Type 2 diabetes has reached epidemic proportions in adults and youths. Persistent organic pollutants and endocrine-disrupting chemicals (EDCs), such as pesticides, dioxins, and organochlorines, are omnipresent and persist in the environment with potential for human exposure via contaminated air, waterways, soil, and human food supply. EDCs have been correlated with diabetes incidence and risks. Residential proximity to hazardous waste sites (HWS) has been correlated with increased hospital admission rates for diabetes. The study used a sample population (N = 1,724), ages ≥ 12 years from the 2005-2012 Continuous NHANES and HWS data from the National Priorities List of Superfund Sites. The ecosocial theory of disease distribution, and geocoordinates provided theoretical support. Mann-Whitney U test and binary logistic regression analysis were used to investigate the relationship between residence ≤ 1 mile compared with residence >1 mile from a HWS in NHANES surveyed counties of NJ, PA, NY, and CA on the outcome abnormal A1c ≥ 5.7% while controlling the effect of the moderators: abnormal body mass index (BMI), age, sex, and race/ethnicity on the relationship. Participants with a BMI ≥ 28.95 kg/m2 were 1.8 times and persons ≥ 58 years of age were 2.1 times more likely to have an A1c ≥ 5.7%. Also, non-Hispanic Whites residing >1 mile of a HWS had 82.1 % reduced risk of abnormal A1c compared with the same group residing ≤ 1 mile of a HWS. The results forge opportunities for future studies to consider border distance between residence and HWS. In addition, the results may promote positive social change through diabetes risks education, environmental health education, and practices and raise dialogue about social justice and the geographic distribution of hazardous waste sites.

POPs are a group of chemicals that have been extensively studied over the last few years. The main reason that these chemicals have received so much scientific attention is the myriad of negative effects they have on the environment and human health. The properties that cause the deleterious effects include a high molecular stability, rendering them highly persistent. Added to this is the lipophilic and hydrophobic nature of the compounds. POPs will thus tend to bio-accumulate and bio-magnify in the environment, causing a direct threat to humans and wildlife. To address this threat, the Stockholm Convention on Persistent Organic Pollutants, under the supervision of United Nations Environment programme (UNEP), was initiated and became legally binding on 17 May 2004. All countries, including South Africa, which ratified this agreement, will be expected to monitor and regulate the formation of POPs. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are all members of the dioxin-like family of POPs. This family of chemicals pose serious health threats such as carcinogenic effects and negative effects on reproduction. These substances, with the exception of PCBs, are formed unintentionally as by-products of industrial and thermal processes. One of the main sources of dioxin-like chemicals is medical waste incinerators. In this project the area surrounding a medical waste incinerator was monitored using a bio-assay technique. The determination of dioxin concentrations is usually preformed by chemical analysis, however, bio-assays have proven themselves to be a cheaper and time-saving screening method. The Toxic Equivalency Quotient (TEQs) determined through bio-assays can support chemical analysis in determining biologically-relevant risk assessments since bio-assay data has ecotoxicological relevance. These assays represent an integrated biological response to chemical pollutants, where biological effects are accounted for which is not possible in chemical analyses. One of the bio-assays used in the determination of the dioxin-like chemical TEQ is the H411 E reporter gene bio-assay. This assay is based on the Ah-receptor mediated toxicity of dioxin-like chemicals. Using this technique the TEQs for areas surrounding an active incinerator were determined, to indicate the distribution of these substances. The TEQs for the soil samples collected ranged between nondetectable and 154 ngTEQ/kg. There was no clear distributional pattern and the total organic carbon content in the soil did not seem to play a crucial role in the distribution of dioxin-like chemicals. Although a decrease in soil tillage showed a corresponding increase in TEQ. The predominant wind direction was taken into account but no correlation could be seen. However, meteorological parameters such as the ambient temperature and low precipitation in the area may have contributed to lower TEQ values. Cytotoxicity excluded data points and the phenomenon has to be addressed. High TEQ values in a residential area where free-range chickens are raised pose a serious concern to the level of dietary dioxin-like chemical intake. Eggs in the area could theoretically contain between 2.75 and 28.75 pgTEQ/g egg fat. Further studies are needed to determine how much dioxin-like chemicals are being transferred to humans through the consumption of free-range eggs
Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

Multivariate modeling techniques are successfully used in different areas of environmental research because of their ability to process large data sets. The main objective of their application lies in the determination of data structures and hidden information which account for the data set variability. This thesis work seeks to explore the application of the positive matrix factorization (PMF) technique to different geochemical data sets on three spatial scales: local, pan-regional and pan-European. In particular, we focus on PMF identification of pollutants/contamination sources (e.g., anthropogenic and natural pollution) and chemical/physical processes (e.g., mineralization, weathering and corrosion) characterizing the data sets under examination. PMF analysis was carried out on four data sets with different spatial scale:  at local scale, geochemical characteristics of soil samples at the abandoned Coren del Cucì mine dump were examined. A GIS-based approach was also combined with PMF results for a better source resolution. Five factors were determined: (i) two geo-morphological backgrounds characteristic of the area outside the dump; (ii) a source of mineralization situated inside the waste disposal area; and (iii) two different geochemical anomaly zones;  at a national level, eleven alpine lakes site in the Northern Italy were considered. X-ray fluorescence analyses on lake sediments were evaluated by PMF. Four interpretable mineralogical/chemical features were identified: (i) phosphate and sulphur source; (ii) carbonates; (iii) silicates; and (iv) heavy metal-bearing minerals. Also, to properly modify input information, a new PMF factor was determined, explaining a possible Pb contamination source;  in the pan-regional context, sediments of the Danube River basin, which cover an area of 817.000 km2, flowing through nine European countries, were analysed. The objective was to draw out information about the natural vs. anthropogenic origin of heavy metals and to determine the role of tributaries. Three factors were identified: (i) a carbonate component characterized by Ca and Mg; (ii) an alumino-silicate component dominated by Si and Al content and the presence of some metals attributed to natural processes; (iii) an anthropogenic source identified by Hg, S, P and some heavy metals load. Considering only the tributaries input, an additional source probably attributed to the use of fertilizers in agriculture was determined;  finally, a pan-European data set comprising sewage sludge from European waste water treatment plants was obtained. The final objective was to link the silver content to the increasingly use of silver nanoparticles in a variety of house-hold and personal care products. Here, method validation procedure was applied to the measured elements in order to compute correct uncertainties to be used in PMF application. The four resulting factors could be described by: (i) copper dissolution from water pipe lines; (ii) engineered silver nanoparticles load; (iii) anthropogenic influence suggested by the presence of different metals; and (iv) iron variation due to the use of this element for phosphorus removal in sewage sludge. These studies provide first evidence that PMF could be successfully applied to geochemical data sets at different spatial scale.

Lab scale reactors were used to measure the emissions of non-methane organic compounds (NMOCs)and hazardous air pollutants (HAPs) from decomposing refuse. Reactors containing municipal solid waste (MSW) as well as reactors containing individual waste components (paper waste, yard waste, food waste, household hazardous waste) were operated under anaerobic conditions with leachate neutralization and recycle. Decomposition of MSW under aerobic and nitrate-reducing conditions was also studied. NMOC yields ranged from 0.016 mg-C/dry gm (paper) to 0.347 mg-C/dry gm (food). The data suggest that volatilization, or air stripping, is the primary mechanism of NMOC release, although the decomposition process also contributes.

2013 - 2014
As a consequence of the rapid growth of population in urban areas, water use and reuse has become a major concern, leading to an urgent imperative of developing effective and affordable technologies for the treatment of water and wastewater. Traditional methods for water treatment are usually based on physical and biological processes but, unfortunately, some organic pollutants, classified as bio-recalcitrant, are not biodegradable. In this way heterogeneous photocatalysis may become an effective water treatment technology to remove organic pollutants hardly oxidised by conventional techniques. Photocatalysis represents one of the main challenges in the field of treatment and decontamination of water and air, because it is able to work at ambient temperature and atmospheric pressure. Heterogeneous photocatalysis is a catalytic process that uses the energy associated to a light source to activate a catalyst with semiconducting properties. The most common used photocatalyst is titanium dioxide (TiO2), which is able to oxidize a wide range of toxic organic compounds to harmless compounds such as CO2 and H2O. However, the following major factors limit both photocatalytic efficiency and activity of TiO2: a) the band gap of anatase TiO2 is 3.2 eV, i.e. it absorbs light in the UV region, so that only a small portion (5%) of sunlight can be used for a photocatalytic process. This is a great limitation in its use as photocatalyst for the conversion of solar into chemical energy; b) as in all semiconductors, photogenerated electron-hole couples undergo fast recombination in competition with charge transfer to adsorbed species on the catalyst surface; c) the use of slurry reactors limits the industrial applications of photocatalysis, since the necessary separation of catalyst powders after liquid phase reactions is troublesome and expensive. In this context, during this PhD project different routes have been explored to go beyond these limitations: 1. With respect to the use of visible light irradiation, doping with anions belonging to the p-block was investigated in recent years to sensitize TiO2 towards visible light, either by introducing newly created mid-gap energy states, or by narrowing the band gap itself. However, the role of titania dopants such as N, C, B, S, P, I and F is still not completely understood. The insertion of dopants in the crystalline structure of TiO2 may induce light absorption in the visible region, but also increases the rate of the undesired recombination of photogenerated charge carriers. This effect becomes relatively lower if the crystallinity of the oxide structure is higher... [edited by Author]
XIII n.s.

Thesis submitted in fulfilment of the requirements for the degree Master of Technology: Chemical Engineering in the Faculty of Engineering at the Cape Peninsula University of Technology 2014
Environmental legislation focusing on wastewater disposal in industries that utilise cyanide and/or cyanide-related compounds has become increasingly stringent worldwide, with many companies that utilise cyanide products required to abide by the Cyanide International Code associated with the approval of process certifications and management of industries which utilise cyanide. This code enforces the treatment or recycling of cyanide-contaminated wastewater. Industries such as those involved in mineral processing, photo finishing, metal plating, coal processing, synthetic fibre production, and extraction of precious metals, that is, gold and silver, contribute significantly to cyanide contamination in the environment through wastewater. As fresh water reserves throughout the world are low, cyanide contamination in water reserves threatens not only the economy, but also endangers the lives of living organisms that feed from these sources, including humans. In the mining industry, dilute cyanide solutions are utilised for the recovery of base (e.g. Cu, Zn, Ni, etc.) and precious metals (e.g. Au, Ag, etc.). However, for technical reasons, the water utilised for these processes cannot be recycled upstream of the mineral bioleaching circuit as the microorganisms employed in mineral bioleaching are sensitive to cyanide and its complexes, and thus the presence of such compounds would inhibit microbial activity, resulting in poor mineral oxidation. The inability to recycle the water has negative implications for water conservation and re-use, especially in arid regions. A number of treatment methods have been developed to remediate cyanide containing wastewaters. However, these chemical and physical methods are capital intensive and produce excess sludge which requires additional treatment. Furthermore, the by-products that are produced through these methods are hazardous. Therefore, there is a need for the development of alternative methods that are robust and economically viable for the bioremediation of cyanide-contaminated wastewater. Biological treatment of free cyanide in industrial wastewaters has been proved a viable and robust method for treatment of wastewaters containing cyanide. Several bacterial species, including Bacillus sp., can degrade cyanide to less toxic products, as these microorganisms are able to use the cyanide as a nitrogen source, producing ammonia and carbon dioxide. These bacterial species secrete enzymes that catalyse the degradation of cyanide into several end-products. The end-products of biodegradation can then be utilised by the microorganisms as nutrient sources. This study focused on the isolation and identification of bacterial species in wastewater containing elevated concentrations of cyanide, and the assessment of the cyanide biodegradation ability of the isolates. Thirteen bacterial isolates were isolated from electroplating wastewater by suppressing the growth of fungal organisms and these species were identified as species belonging to the Bacillus genus using the 16S rDNA gene. A mixed culture of the isolates was cultured in nutrient broth for 48 hours at 37°C, to which FCN as KCN was added to evaluate the species‟ ability to tolerate and biodegrade cyanide in batch bioreactors. Subsequently, cultures were supplemented solely with agro-waste extracts, that is, Ananas comosus extract (1% v/v), Beta vulgaris extract (1% v/v), Ipomea batatas extract (1% v/v), spent brewer‟s yeast (1% v/v) and whey (0.5% w/v), as the primary carbon sources. Owing to the formation of high ammonium concentration from the cyanide biodegradation process, the nitrification and aerobic denitrification ability of the isolates, classified as cyanide-degrading bacteria (CDB) was evaluated in a batch and pneumatic bioreactor in comparison with ammonia-oxidising bacteria (AOB). Furthermore, the effects of F-CN on the nitrification and aerobic denitrification was evaluated assess the impact of F-CN presence on nitrification. Additionally, optimisation of culture conditions with reference to temperature, pH and substrate concentration was evaluated using response surface methodology. Using the optimised data, a continuous biodegradation process was carried out in a dual-stage packed- bed reactor combined with a pneumatic bioreactor for the biodegradation of F-CN and subsequent nitrification and aerobic denitrification of the formed ammonium and nitrates. The isolated bacterial species were found to be gram positive and were able to produce endospores that were centrally located; using the 16S rDNA gene, the species were found to belong to the Bacillus genus. The species were able to degrade high cyanide concentration in nutrient broth with degradation efficiencies of 87.6%, 65.4%, 57.0% and 43.6% from 100 mg F-CN/L, 200 mg F-CN/L, 300 mg F-CN/L, 400 mg F-CN/L and 500 mg F-CN/L respectively over a period of 8 days. Additionally, the isolates were able to degrade cyanide in an agro-waste supported medium, especially in a medium that was supplemented with whey which achieved a degradation efficiency of 90% and 60% from 200 mg F-CN/L and 400 mg F-CN/L, respectively over a period of 5 days. The nitrification ability of the isolates was evaluated and the removal of NH4 +/NO3 - by the CDB and AOB in both shake flasks and pneumatic bioreactor was determined to be pH dependent. The maximum NH4 +/NO3 - removal evaluated over a period of 8 days for CDB and 15 days for AOB, observed at pH 7.7 in shake flasks, was 75% and 88%, respectively, in the absence of F-CN. Similarly, the removal of NH4 +/NO3 - in a pneumatic bioreactor was found to be 97.31% for CDB and 92% for AOB, thus demonstrating the importance of aeration in the designed process. The nitrification by CDB was not inhibited by cyanide loading up to a concentration of 8 mg FCN/ L, while the AOB were inhibited at cyanide loading concentration of 1 mg F-CN/L. The CDB removed the NH4 +/NO3 - in PBSs operated in a fed-batch mode, obtaining efficiencies >99% (NH4 +) and 76 to 98% (NO3 -) in repeated cycles (n = 3) under F-CN (≤8 mg F-CN/L). The input variables, that is, pH, temperature and whey-waste concentration, were optimised using a numerical optimisation technique where the optimum conditions were found to be: pH 9.88, temperature 33.60 °C and whey-waste concentration 14.27 g/L, under which 206.53 mg CN-/L in 96 h can be biodegraded by the microbial species from an initial cyanide concentration of 500 mg F-CN/L. Furthermore, using the optimised data, cyanide biodegradation in a continuous mode was evaluated in a dual-stage packed-bed bioreactor connected in series to a pneumatic bioreactor system used for simultaneous nitrification including aerobic denitrification. The whey-supported Bacillus sp. culture was not inhibited by the free cyanide concentration of up to 500 mg F-CN/L, with an overall degradation efficiency of ≥99% with subsequent nitrification and aerobic denitrification of the formed ammoniu and nitrates over a period of 80 days.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
FAPESP:97/07964-0

Nowadays with developing of all parts of human society such as industries, irrigations, cities, etc., the need for fresh water is increasing. There are lots of pollution sources that affect our fresh water resources. In order to have sustainable development and save our fresh water resources for current and future generations, we have to monitor steadily our projects and environments to preserve our water resources from pollution sources. In this thesis, I have general overview on pollutions come from landfills and municipal wastes to our groundwater resources around the world and how we can preserve our resources from pollutions with using of some approaches that come in directives. In order to summarize this research, in the first step, I will discuss about groundwater definition in academic literatures and its different aspects, the importance of it as fresh water resources to cities, industries and agricultural users and. Then I will discuss about different parameters and elements which are caused pollution on groundwater resources. After, I will introduce some landfill case studies around the world. Finally, I will provide some criteria which are prevented our groundwater resources from different pollutions with using of some directives and rules.