Cities are sources of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), to surrounding regions and beyond. A spatially resolved, (5×5 km2), dynamic contaminant fate model named Spatially Oriented or SO-MUM was developed by coupling the fugacity based Multimedia Urban Model (MUM) (Diamond et al., 2001; Diamond et al., 2010c) and the Boundary Layer Forecast Model and Air Pollution Prediction System (BLFMAPS) which was developed at Environment Canada (Daggupaty et al., 2006). MUM was updated to contain a revised surface film sub-model which takes into account the dynamic nature of surface films. SO-MUM was illustrated by application to the City of Toronto, Canada. Spatially resolved air emissions of Σ88PCB were estimated to be ~230 (40-480) kg y-1, 280 (50-580) g y-1 km-2, and 90 (16-190) mg y-1 capita-1 and Σ26PBDE were estimated to be 28 (6-63) kg y-1, 34 (7-77) g y-1 km-2 and 11 (2-25) mg y-1 capita-1. These emissions were back-calculated from measured air concentrations and spatial chemical mass inventories yielding emission rates per mass inventory of 0.4 (0.05-1.6) and 0.1 (0.01-0.7) g kg-1inventory y-1, for Σ88PCBs and Σ26PBDEs, respectively. Approximately 30% and 16% of PCB and PBDE emissions emanate from the city’s downtown. Air advection accounted for ~95% (PCB) and ~70% (PBDE) of total air emission losses with the remaining balance depositing to the city. The metric “Urban Travel Distance” or UTD was introduced for quantifying the extent of an urban plume resulting from spatially heterogeneous emissions. For PCBs and PBDEs the UTDs were ~25 and ~30 km. The updated surface film sub-model indicated that films “bounce” higher vapor pressure semi-volatile organic compounds (SVOCs) back into the air but they act as a transient sink from air for lower vapor pressure SVOCs, thereby facilitating transport to surface waters. Model calculations suggest that if the PCB inventory is reduced, volatilization from near-shore Lake Ontario will become a net source of PCBs to air, but that neither near-shore Lake Ontario nor soil would become a significant volatilization PBDE source to air.

Cities are sources of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), to surrounding regions and beyond. A spatially resolved, (5×5 km2), dynamic contaminant fate model named Spatially Oriented or SO-MUM was developed by coupling the fugacity based Multimedia Urban Model (MUM) (Diamond et al., 2001; Diamond et al., 2010c) and the Boundary Layer Forecast Model and Air Pollution Prediction System (BLFMAPS) which was developed at Environment Canada (Daggupaty et al., 2006). MUM was updated to contain a revised surface film sub-model which takes into account the dynamic nature of surface films. SO-MUM was illustrated by application to the City of Toronto, Canada. Spatially resolved air emissions of Σ88PCB were estimated to be ~230 (40-480) kg y-1, 280 (50-580) g y-1 km-2, and 90 (16-190) mg y-1 capita-1 and Σ26PBDE were estimated to be 28 (6-63) kg y-1, 34 (7-77) g y-1 km-2 and 11 (2-25) mg y-1 capita-1. These emissions were back-calculated from measured air concentrations and spatial chemical mass inventories yielding emission rates per mass inventory of 0.4 (0.05-1.6) and 0.1 (0.01-0.7) g kg-1inventory y-1, for Σ88PCBs and Σ26PBDEs, respectively. Approximately 30% and 16% of PCB and PBDE emissions emanate from the city’s downtown. Air advection accounted for ~95% (PCB) and ~70% (PBDE) of total air emission losses with the remaining balance depositing to the city. The metric “Urban Travel Distance” or UTD was introduced for quantifying the extent of an urban plume resulting from spatially heterogeneous emissions. For PCBs and PBDEs the UTDs were ~25 and ~30 km. The updated surface film sub-model indicated that films “bounce” higher vapor pressure semi-volatile organic compounds (SVOCs) back into the air but they act as a transient sink from air for lower vapor pressure SVOCs, thereby facilitating transport to surface waters. Model calculations suggest that if the PCB inventory is reduced, volatilization from near-shore Lake Ontario will become a net source of PCBs to air, but that neither near-shore Lake Ontario nor soil would become a significant volatilization PBDE source to air.

No description available.

Since 2008, large numbers of Nile crocodile (Crocodylus niloticus) carcasses were found in the Kruger National Park (KNP), South Africa. Most of the crocodile carcasses were found in the Olifants Gorge, which is situated below the Letaba and Olifants river confluence, before the Mozambique border and Massingir Dam. The Massingir Dam is an important resource and it plays a significant role in the welfare of the local Mozambican population. Autopsies performed on the crocodiles indicated that the adipose tissue colour changed from normal white to yellow and this is usually a sign of pansteatitis. Pansteatitis is caused by lipid peroxidation in an organism and it is characterised by the lack of vitamin E. This disease is recognisable by the hardening of the fatty tissue and yellow discolouration, and is mostly associated with aquatic organisms from polluted ecosystems. There are speculations that the crocodile fatalities may be associated with the Massingir Dam that backed up into the Olifants Gorge after flooding. After the dam was reconstructed, it flooded the Olifants Gorge, causing it to act like a localised sediment trap as the water flow slowed down and as a result, caused pollutants to build-up. Sediment samples were collected from selected rivers and ponds within the KNP. These samples were analysed for selected elements, persistent organic pollutants (POPs), and polycyclic aromatic hydrocarbons (PAHs). The sediment samples were analysed in Norway for POPs and PAHs with the use of a high-resolution gas chromatography/mass spectrometry (GC/MS) and the heavy metals were analysed in South Africa with the use of inductively-coupled plasma mass spectrometry (ICP/MS). In order to identify which elements may have affected the health of the crocodiles, a series of sediment quality indices were used. These indices made it possible to determine which elements may have been involved. The order of probability of heavy metals causing harm was Se>As>Ni>Cr>Cu>I>V>Mn>Co>Fe>Cd>Hg>Zn>Pb>Ba>U. The data was compared to selected international guidelines. All the information was used to determine which of the sampled sites had the highest contamination. The sites sampled with the highest concentrations were in the Crocodile, Nkomati, Olifants, and Letaba Rivers. Concentrations of the elements, POPs, and PAHs were also quantifiable in the Olifants Gorge. The following elements (Fe, Co, Cu, Cr, Pb, V, As, and Ni) were quantified at elevated levels and may therefore have caused negative effects on the crocodiles in the Olifants Gorge. These elevated concentrations, in combination with the dramatic change in the physical environment due to the dam, could have added additional stress that may have contributed to the observed crocodile mortalities in the Olifants Gorge. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

Since 2008, large numbers of Nile crocodile (Crocodylus niloticus) carcasses were found in the Kruger National Park (KNP), South Africa. Most of the crocodile carcasses were found in the Olifants Gorge, which is situated below the Letaba and Olifants river confluence, before the Mozambique border and Massingir Dam. The Massingir Dam is an important resource and it plays a significant role in the welfare of the local Mozambican population. Autopsies performed on the crocodiles indicated that the adipose tissue colour changed from normal white to yellow and this is usually a sign of pansteatitis. Pansteatitis is caused by lipid peroxidation in an organism and it is characterised by the lack of vitamin E. This disease is recognisable by the hardening of the fatty tissue and yellow discolouration, and is mostly associated with aquatic organisms from polluted ecosystems. There are speculations that the crocodile fatalities may be associated with the Massingir Dam that backed up into the Olifants Gorge after flooding. After the dam was reconstructed, it flooded the Olifants Gorge, causing it to act like a localised sediment trap as the water flow slowed down and as a result, caused pollutants to build-up. Sediment samples were collected from selected rivers and ponds within the KNP. These samples were analysed for selected elements, persistent organic pollutants (POPs), and polycyclic aromatic hydrocarbons (PAHs). The sediment samples were analysed in Norway for POPs and PAHs with the use of a high-resolution gas chromatography/mass spectrometry (GC/MS) and the heavy metals were analysed in South Africa with the use of inductively-coupled plasma mass spectrometry (ICP/MS). In order to identify which elements may have affected the health of the crocodiles, a series of sediment quality indices were used. These indices made it possible to determine which elements may have been involved. The order of probability of heavy metals causing harm was Se>As>Ni>Cr>Cu>I>V>Mn>Co>Fe>Cd>Hg>Zn>Pb>Ba>U. The data was compared to selected international guidelines. All the information was used to determine which of the sampled sites had the highest contamination. The sites sampled with the highest concentrations were in the Crocodile, Nkomati, Olifants, and Letaba Rivers. Concentrations of the elements, POPs, and PAHs were also quantifiable in the Olifants Gorge. The following elements (Fe, Co, Cu, Cr, Pb, V, As, and Ni) were quantified at elevated levels and may therefore have caused negative effects on the crocodiles in the Olifants Gorge. These elevated concentrations, in combination with the dramatic change in the physical environment due to the dam, could have added additional stress that may have contributed to the observed crocodile mortalities in the Olifants Gorge. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

In the transition to a sustainable energy supply there is an increasing need to use biomass for replacement of fossil fuel. A key challenge is to utilize biomass conversion technologies in an environmentally sound manner. Important aspects are to minimize potential formation of persistent organic pollutants (POPs) such as dioxins and dioxin-like compounds. This thesis involves studies of formation characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) in microwave-assisted pyrolysis (MAP) and torrefaction using biomass as feedstock. The research focuses are on their levels, distributions, fingerprints (homologue profiles and isomer patterns) and the underlying formation pathways. The study also included efforts to optimize methods for extracting chlorinated aromatic compounds from thermally treated biomass. The overall objective was to contribute better understanding on the formation of dioxins and dioxin-like compounds in low temperature thermal processes. The main findings include the following: Pressurized liquid extraction (PLE) is applicable for simultaneous extraction of PCDDs, PCDFs, PCNs, polychlorinated phenols and benzenes from thermally treated wood. The choice of solvent for PLE is critical, and the extraction efficiency depends on the degrees of biomass carbonization. In MAP experiments PCDDs, PCDFs and PCNs were predominantly found in pyrolysis oils, while in torrefaction experiments they were mainly retained in solid chars with minor fractions in volatiles. In both cases, highly chlorinated congeners with low volatility tended to retain on particles whereas the less chlorinated congeners tended to volatize into the gas phase. Isomer patterns of PCDDs, PCDFs and PCNs generated in MAP were more selective than those reported in combustion processes. The presence of isomers with low thermodynamic stability suggests that the pathway of POPs formation in MAP may be governed not only by thermodynamic stabilities but also by kinetic factors. Formation of PCDDs, PCDFs and PCNs depends not only on the chlorine contents in biomass but also the presence of metal catalysts and organic/metal-based preservatives. Overall, the results provide information on the formation characteristics of PCDDs, PCDFs and PCNs in MAP and torrefaction. The obtained knowledge is useful regarding management and utilization of thermally treated biomass with minimum environmental impact.

Incineration with energy recovery is the main disposal strategy for waste that cannot be reused or recycled, and a well-established source of energy in Europe, especially in Sweden where 2.2 Mtonnes of waste including domestic and imported municipal solid waste (MSW) and waste wood (WW) were combusted during 2015. However, owing to its inherent heterogeneous composition, inclusion of such waste in Waste-to-energy (WtE) technologies is challenging. These heterogeneities may lead to operationally-related issues in the WtE facilities and contribute to toxic emissions, which can be reduced by waste pre-treatment technologies.    This thesis examines the variations in the composition of MSW and WW streams used as a fuel supply in WtE facilities after undergoing waste pre-treatment technologies, and the effect of fuel composition on its combustion behaviour and formation of persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The overall objective is to contribute to a more thorough understanding of the selection of waste pre-treatment technologies to mitigate harmful emissions into the atmosphere when waste fuels are combusted in WtE facilities.    This thesis describes the high variability of contaminants in domestic and imported WW and suggests adaptation of WW pre-treatment techniques to produce fuels with a low potential for generating pollutants. A comparison of mechanical solid waste pre-treatments revealed that screening and shredding is more efficient than extrusion for reducing emissions of pollutants such as PCDDs and PCDFs in combustion. The evaluation of the combustion behaviour of MSW-based fuels showed a three-stage oxidative decomposition, and an acceleration of the decomposition of the MSW compared to the lignocellulosic materials, which may be attributed to the presence of food waste and plastics in the MSW. Combustion tests of fuel blends containing WW and MSW-based fuels with different food waste content suggested that WW, not food waste content, is the key factor for the formation of PCDDs, PCDFs, and polychlorinated biphenyls (PCB), benzenes (PCBzs) and phenols (PCPhs). Torrefaction may be a suitable technology for improving the properties of waste as a fuel e.g. due to its low PCDD and PCDF emissions. / Förbränning med energiåtervinning är det huvudsakliga sättet att ta hand om avfall som inte kan återanvändas eller återvinnas. Det är en väletablerad energikälla i Europa och särskilt i Sverige där 2,2 miljoner ton avfall, däribland inhemskt och importerat hushållsavfall och returträ, förbrändes under 2015. På grund av den heterogena sammansättningen hos hushållsavfall och returträ är förbränning av dessa material i anläggningar med energiåtervinning (så kallade WtE-anläggningar) förknippade med en del driftsrelaterade utmaningar. Det kan även ge upphov till miljöfarliga utsläpp, som dock kan reduceras genom förbehandling av avfallet. I denna avhandling har variationer i sammansättningen hos hushållsavfall och returträ som förbränns i WtE-anläggningar undersökts. Effekten av bränslemixens sammansättning och ev förbehandling på bränslets förbränningsegenskaper samt bildning av långlivade organiska föroreningar (så kallade POPar) såsom polyklorerade dibenso-p-dioxiner och polyklorerade dibensofuraner vid förbränning har utvärderats. Det övergripande målet är att bidra till en djupare förståelse av hur valet av förbehandlingsteknik för avfall kan bidra till att minska skadliga utsläpp till luft när avfallsbränslen förbränns i WtE-anläggningar. Denna avhandling beskriver den stora variabiliteten av metall- och materialföroreningar i inhemskt och importerat returträ och föreslår förbehandlingstekniker för att producera bränslen med låg potential att generera föroreningar. En jämförelse av mekaniska förbehandlingstekniker visade att mekanisk sönderdelning och separering (krossning och siktning) är mer effektivt än s.k. högtrycks-pressning för att minska utsläppen av föroreningar som dioxiner och furaner vid förbränning. Utvärderingen av bränslemixar innehållande hushållsavfall uppvisade en oxidativ nedbrytning i tre steg vid förbränning, och en accelererad nedbrytning av avfallsmaterialet jämfört med vedmaterialet i bränslet, troligen som effekt av innehållet av matavfall och plast i hushållsavfallet. Förbränningsförsök med bränsleblandningar av returträ och hushållsavfall med olika innehåll av matavfall visade att mängden returträ, och inte mängden matavfall, är den viktigaste faktorn för bildning av dioxiner, furaner, klorbifenyler, klorbensener, och klorfenoler. Torrefiering kan vara en lämplig teknik för att förbättra avfallets bränsleegenskaper, t.ex. på grund av dess låga emissioner.

Philosophiae Doctor - PhD / Persistent organic pollutants (POPs) are very tenacious wastewater contaminants with negative impact on the ecosystem. The two major sources of POPs are wastewater from textile industries and pharmaceutical industries. They are known for their recalcitrance and circumvention of nearly all the known wastewater treatment procedures. However, the wastewater treatment methods which applied advanced oxidation processes (AOPs) are documented for their successful remediation of POPs. AOPs are a group of water treatment technologies which is centered on the generation of OH radicals for the purpose of oxidizing recalcitrant organic contaminants content of wastewater to their inert end products. Circumvention of the reported demerits of AOPs such as low degradation efficiency, generation of toxic intermediates, massive sludge production, high energy expenditure and operational cost can be done through the application of the combined AOPs in the wastewater treatment procedure. The resultant mineralisation of the POPs content of wastewater is due to the synergistic effect of the OH radicals produced in the combined AOPs. Hydrodynamic cavitation is the application of the pressure variation in a liquid flowing through the venturi or orifice plates. This results in generation, growth, implosion and subsequent production of OH radicals in the liquid matrix. The generated OH radical in the jet loop hydrodynamic cavitation was applied as a form of advanced oxidation process in combination with hydrogen peroxide, iron (II) oxides or the synthesized green nano zero valent iron (gnZVI) for the treatment of simulated textile and pharmaceutical wastewater.

A distribuição espacial e o histórico deposicional de poluentes orgânicos persistentes (POPs) em sedimentos foram avaliados no ecossistema marino-estuarino da Ilha do Marajó, Pará. Os pesticidas predominantes nos sedimentos da camada superficial foram os HCHs (<0,04 e 0,90 ng g-1) e DDTs (<0,02 - 2,72 ng g-1), em peso seco. PCBs e PBDEs não foram detectados. HCHs predominaram no Estuário do Rio Paracauari indicando uso recente provavelmente relacionado à atividade madeireira. DDTs foram detectados na Praia do Pesqueiro e nos testemunhos sedimentares (<0,02 - 12,31 ng g-1 peso seco) do Mercado, Fazenda e Paracauari. Os valores máximos de DDT ocorreram entre 1982 e 2008 e são associados com campanhas de saúde púbica. Há uma redução gradativa até o presente que coincide com a substituição do DDT por piretróides. A razão &#931;DDDs / &#931;DDEs, predominantemente < 1, indicou a ocorrência de processos decomposicionais aeróbicos. No geral, as condições ambientais não favorecem o acúmulo de pesticidas nos sedimentos, sendo que os valores estão abaixo do limite provável para causar efeitos adversos exceto para HCHs no Estuário do Rio Paracauari. O presente trabalho estabeleceu a distribuição de POPs na Ilha do Marajó e poderá contribuir para o processo de gestão costeira e ambiental da região. / The spatial distribution and depositional history of persistent organic pollutants (POPs) in sediments were evaluated in marino-estuarine ecosystem of Marajó Island, Pará. The predominant pesticides in sediments of the surface layer were HCHs (<0.04 and 0, 90 ng g-1) and DDTS (<0.02 to 2.72 ng g-1) by dry weight. PCBs and PBDEs weren\'t detected. HCHs predominated in Paracauari Estuary indicating recent use probably related to logging. DDTs were detected in Praia do Pesqueiro and sediment cores (<0.02 to 12.31 ng g-1 dry weight) Mercado, Fazenda and Paracauari. Maximum levels of DDT residues occurred between 1982 and 2008 and are associated with pubic health campaigns. There is a gradual reduction up to the present which coincides with the substitution of the DDTs by pyrethroids. The ratio &#931;DDDs / &#931;DDEs predominantly < 1 indicated the occurrence of decomposicional processes under aerobic conditions. Overall, the environmental conditions do not favor the accumulation of pesticides in sediments, and the values are below the threshold likely to cause adverse effects except for HCHs in Paracauari Estuary. This work established the distribution of POPs in Marajó Island and could contribute to the process of coastal and environmental management in the region.

Apesar de os defensivos agrícolas atualmente classificados como Poluentes Orgânicos Persistentes (POPs) terem sua produção e uso banidos na maior parte do mundo desde a década de 1980, o gerenciamento de estoques remanescentes permanece um desafio até a atualidade. Com estimativas que variam entre 500 mil (FAO, 2015) e 2 milhões de toneladas (VIJGEN et al., 2011), poucas informações sobre seu efetivo gerenciamento e destruição são encontradas nas principais bases de dados acadêmicas sobre o tema e nos documentos oficiais da Convenção de Estocolmo sobre Poluentes Orgânicos Persistentes. O Brasil integra a lista de signatários da Convenção, mas a fabricação, o armazenamento e o uso dos agrotóxicos POPs foram proibidos em 1985, por meio da Portaria do Ministério da Agricultura nº 329. Este abrupto banimento do armazenamento colocou o agricultor brasileiro imediatamente fora da lei, uma vez que não foram planejadas medidas e procedimentos legais para dar destino adequado aos produtos que ainda estivessem em estoque nas propriedades rurais. De forma independente da Convenção de Estocolmo e das ações nacionais relacionadas a este tratado, dois estados brasileiros elaboraram programas para o levantamento de estoque dos defensivos agrícolas banidos e planejamento de sua destinação. Finalizado em 2013, o Paraná incinerou cerca de 1.200 toneladas que estavam estocadas em mais de 2.000 propriedades rurais do estado. São Paulo finalizou o inventário em 2012, resultando em 420 toneladas estocadas em aproximadamente 330 propriedades rurais. O grupo de trabalho paulista planejou as etapas seguintes e em abril de 2016, o projeto se encontrava em fase de alocação de recursos para execução das fases finais de acondicionamento, transporte e destinação. A proposta deste projeto de pesquisa é apresentar como Paraná e São Paulo gerenciaram os estoques remanescentes de agrotóxicos banidos há décadas, avaliando como os grupos de trabalho foram formados, as normativas de apoio utilizadas, como foram realizadas as etapas de levantamento de inventário e de que forma foram planejadas, financiadas, comunicadas e executadas as etapas de coleta, acondicionamento, transporte e destinação. Dessa forma, busca-se contribuir para um aumento de conhecimento prático sobre o tema e para a construção de uma política pública para gerenciamento de agrotóxicos banidos em outros estados brasileiros. / Although the pesticides currently classified as Persistent Organic Pollutants (POPs) have had their production and use banned in most of the world since the 1980s, the management of remaining stocks remains a challenge to the present. With estimates ranging from 500,000 (FAO, 2015) and 2 million tons (Vijgen et al., 2011), little information about its effective management and destruction are found in major academic databases on the subject and official documents of the Stockholm Convention on Persistent Organic Pollutants. Brazil is one of the signatories but the manufacture, storage and use of pesticides POPs were banned in 1985 by the Ministry of Agriculture Decree No. 329. However, this abrupt ban put the Brazilian farmers immediately outside the law since the government did not plan measures and legal procedures to give proper destination to the products that were still in stock on farms. Independently of the Stockholm Convention and the National Plans related to this treaty, two Brazilian states have developed programs to inventory banned pesticides and plan their destination. Finished in 2013, Paraná State incinerated about 1,200 tons that had been stored in more than 2,000 rural properties. Sao Paulo finished its inventory in 2012 resulting in 420 tons stored in about 330 rural properties. The São Paulo working group has planned the next steps and, in April 2016, the project was waiting for resource in order to implement the final stages of packaging, transport and disposal. The purpose of this research is to present as Parana and Sao Paulo managed the remaining stocks of banned pesticides evaluating how the working groups were formed, the support normative used, how the inventory has been planned and carried out and how the projects have financed, communicated and executed the steps of collection, packaging, transportation and disposal. Thus, it is expected to contribute to increase the practical knowledge on the topic and to construct a public policy for pesticide management banned in other Brazilian states.