In the case of fires frequently wide range of inhomogeneous material is burnt. A lot of combustion products arise during this event, which may adversely affect the environment. Most often detected compounds are carbon dioxide, carbon monoxide, sulfur dioxide, sulphane, hydrogen cyanide, nitrous gases and also organic compounds, which show adverse effects for organism. It is possible to identify and quantify most of them by chemical analysis, but their impact on the ecosystem is not predictable on the basis of these results. An effective tool to predict the impact of combustion products on the ecosystem are ecotoxicity tests. In this thesis, the water leachates of samples from fire places were prepared and subjected to ecotoxicological tests. Two alternative test of ecotoxicity on aquatic organisms were used: the first on the organism Thamnocephalus platyurus (ThamnotoxkitFTM) and the second on the organism Daphnia magna (DaphtoxkitFTM). Another testing aquatic organism was Artemia salina. Ecotoxicity was also tested using a standard phytotoxicity tests; white mustard (Sinapis alba) and white onion (Allium cepa) root growth inhibition tests and lesser duckweed (Lemna minor) growth inhibition test. On the basis of obtained ecotoxicological values LC (EC, IC)50 the impact of matrices from fire places on the ecosystem was evaulated.

No description available.

Nitrogen-, sulfur-, and oxygen-substituted heterocyclic polyaromatic hydrocarbons (heterocyclic PAHs) are ubiquitous in all environmental compartments, often co-occurring with their unsubstituted carbocyclic analogues. However, they have received little attention in the hazard assessment of contaminated sites and little is known about their fate and impacts. Due to their higher polarity resulting from the presence of electronegative atoms possessing lone electron pairs, most heterocycles are expected to be less toxic and bioaccumulative than their homocyclic counterparts, which is perhaps why research on their hazard and fate is much more limited. If this assumption is not true (e.g., because factors other than polarity/hydrophobicity drive their hazard), this may lead to an underestimation of the risks posed by contaminated sites or emissions. Therefore, the main objectives of this thesis are (1) to improve the understanding of the physicochemical properties, biodegradability, ecotoxicity, bioaccumulation, and mobility of these compounds in environmental contexts, (2) to evaluate the effectiveness of different modeling approaches in accurately predicting their properties, and (3) to tackle experimental barriers by designing robust techniques that can produce reliable and reproducible data output in the long run. From the large family of heterocycles, structurally comparable representative compounds with log KOW values (as a measure of hydrophobicity) ranging over four orders of magnitude were selected as model structures. First, the most environmentally relevant physicochemical properties of heterocyclic PAHs were investigated, including water solubility (SW), n-octanol-water partition coefficient (KOW), and organic carbon-water partition coefficient (KOC). The effect of molecular size, type and number of heteroatoms on the solubility and partition coefficients was investigated. These properties were then used to test the performance of in silico models, including Quantitative Structure-Property Relationship (QSPR), Polyparameter Linear Free Energy Relationship (pp-LFER), and Conductor-like Screening Model for Realistic Solvation (COSMO-RS), that predict these properties. A screening-level environmental hazard assessment was performed by integrating the data and evidence from multiple sources. The screening results revealed (i) high hazard for 4- and 5-ring compounds mainly due to high persistence and bioaccumulation potential, (ii) limited availability of experimental data, and (iii) notable uncertainty due to the limited applicability domain of the models, stressing the urgent need for a detailed hazard assessment for this group of compounds. The persistence of heterocyclic PAHs in the environment was assessed experimentally through a series of biodegradation tests under aerobic conditions. These included ultimate biodegradation, primary biodegradation and inoculum toxicity tests at different exposure concentrations. None of the test substances (≥3 rings) were found to be readily biodegradable. Therefore, to stimulate the biodegradation process, the microbial community from a wastewater treatment plant was adapted to a mixture of heterocyclic PAHs and biodegradation tests were performed with either adapted or non-adapted bacteria. Surprisingly, there were trade-offs in bacterial adaptation: a positive outcome (degradation of carbazole) is accompanied by a less desirable outcome (increased sensitivity to toxic effects of benzo[c]carbazole). Four of the compounds were identified as primarily biodegradable, while five compounds showed no evidence of biodegradation in any of the tests, indicating a high potential for environmental persistence. Predictions from mathematical models were also compared with measured results and it was found that the models were only partially successful in predicting the degradation timeframe of the heterocycles tested. Furthermore, the short-term acute aquatic toxicity of heterocyclic PAHs was investigated using three surrogate species from different trophic levels of the aquatic food web, including bacteria (Aliivibrio fischeri), unicellular algae (Raphidocelis subcapitata), and water fleas (Daphnia magna). In order to maintain a stable exposure and to avoid loss of concentration caused mainly due to sorption, the passive dosing method was adapted to routine test protocols. Most of the compounds were identified as highly toxic to the tested organisms, and non-polar narcosis (baseline toxicity) was found to be the most likely mode of toxic action for the tested chemicals. Membrane-water partition coefficients (KMW) of heterocyclic PAHs were also determined by solid-supported lipid membrane binding experiments and modeling. The measured KMW values were closely aligned with the KOW values, suggesting that both may be good descriptors for predicting the baseline toxicity and bioaccumulation potential of the tested heterocyclic PAHs. Lastly, the long-term chronic reproductive toxicity and bioaccumulation of large heterocyclic PAHs were investigated using Daphnia magna as an aquatic model organism. The passive dosing method ensured constant exposure even at very low concentration levels (70 ng L-1 to 68 µg L-1) in large and complex experimental systems. Given the enormous time and effort required to conduct long-term toxicity tests with minimal data output, a method was developed to assess chronic toxicity and bioaccumulation potential in a single test. All four substances tested were highly toxic and bioaccumulative in Daphnia magna. However, daphnids’ fecundity recovered rapidly from the toxic effects of the heterocycles during the depuration period in the absence of chemicals. The Predicted No Effect Concentrations (PNECs) of the test compounds were also estimated from the chronic toxicity data and ranged from 1 to 150 ng L-1 in a freshwater environment. Due to the lack of regulation and attention to these compounds, no systematic environmental monitoring data are available for their concentrations in freshwater. However, environmental concentrations of heterocyclic PAHs appear to be higher than the PNECs, particularly at contaminated sites. Thus, the tested heterocycles are of high concern in terms of risks to ecosystems and human health. Overall, the results of this research not only contribute to a comprehensive understanding and progress in the environmental hazard assessment of heterocyclic PAHs, but also present several methodological advances that can be applied to future testing of other challenging substances commonly referred to as 'difficult-to-test'. / Stickstoff-, schwefel- und sauerstoffsubstituierte heterocyclische polyaromatische Kohlenwasserstoffe (heterocyclische PAK) sind in allen Umweltkompartimenten gegenwärtig und treten häufig zusammen mit ihren homocyclischen Analoga auf. Bei der Gefährdungsbeurteilung kontaminierter Standorte wurde ihnen bisher verhältnismäßig wenig Aufmerksamkeit geschenkt, zudem ist über ihr Verhalten und ihre Ökotoxizität nur wenig bekannt. Aufgrund ihrer höheren Polarität, die auf das Vorhandensein elektronegativer Atome zurückzuführen ist, ging man bislang davon aus, dass die meisten heterocyclischen PAK mobiler und weniger toxisch sind als ihre homocyclischen Pendants, weshalb sie wahrscheinlich bislang vergleichsweise wenig studiert wurden. Sollte die Annahme einer geringeren Toxizität nicht zutreffen, weil beispielsweise andere Mechanismen als die Polarität/Hydrophobie für ihre Gefährdung verantwortlich sind, könnte dies zu einer Unterschätzung der Risiken, die von kontaminierten Standorten oder anderen Emissionen ausgehen, führen. Die Hauptziele dieser Arbeit bestehen daher darin, (1) ein umfassenderes Verständnis der physikalisch-chemischen Eigenschaften, der biologischen Abbaubarkeit, der Ökotoxizität, der Bioakkumulation und der Mobilität dieser Verbindungen in der Umwelt zu erlangen; (2) eine Bewertung verschiedener Modellierungsansätze zur Vorhersage dieser Eigenschaften durchzuführen und (3) experimentelle Hindernisse zu überwinden, indem robustere Techniken entwickelt werden, die langfristig zuverlässige und reproduzierbare Daten liefern können. Aus der sehr breiten Gruppe der heterocyclischen Verbindungen wurden strukturell vergleichbare repräsentative Verbindungen mit unterschiedlichen log KOW-Werten (als Maß für die Hydrophobie), die vier Größenordnungen abdecken, als Modellstrukturen ausgewählt. Zunächst erfolgte eine Untersuchung umweltrelevanter physikalisch-chemischer Eigenschaften dieser heterocyclischen PAK, wie die Wasserlöslichkeit (SW), der n-Octanol-Wasser-Verteilungskoeffizient (KOW) und der Verteilungskoeffizient bezogen auf den organischen Kohlenstoff und Wasser (KOC). Dabei wurden die Auswirkungen von Molekülgröße, Art und Anzahl der Heteroatome auf die Löslichkeit und die Verteilungskoeffizienten systematisch untersucht. Diese experimentell ermittelten Parameter wurden dann verwendet, um die Leistung von In-silico-Modellen zu testen, einschließlich der quantitativen Struktur-Eigenschafts-Beziehung (QSPR), der linearen Polyparameter-Energie-Beziehung (pp-LFER) und des Conductor-like Screening Model for Realistic Solvation (COSMO-RS), die diese Eigenschaften vorhersagen. Zudem wurde eine Umweltverträglichkeitsprüfung auf Screening-Ebene durchgeführt, bei der Daten aus verschiedenen Quellen berücksichtigt wurden. Den Screening-Ergebnissen zufolge ist davon auszugehen, dass kleine Verbindungen mit zwei oder drei Ringen in der Umwelt mobil sind, während größere heterocyclische PAK im Allgemeinen als bioakkumulierbare Stoffe identifiziert wurden, was auf ein erhebliches Gefahrenpotenzial hinweist. Die Persistenz von heterocyclischen PAK wurde experimentell durch eine Reihe von Tests zum biologischen Abbau unter aeroben Bedingungen untersucht. Dazu gehörten Tests zur Mineralisierung, zum biologischen Primärabbau und zur Inokulumtoxizität bei unterschiedlichen Expositionskonzentrationen. Keine der Prüfsubstanzen mit drei oder mehr Kohlenstoffringen erwies sich als biologisch gut/schnell abbaubar. Um den biologischen Abbauprozess zu stimulieren, wurde daher die mikrobielle Gemeinschaft aus einer Kläranlage an das Gemisch heterocyclischer PAK angepasst, wobei die Tests zum biologischen Abbau entweder mit angepassten oder nicht angepassten Bakterien durchgeführt wurden. Überraschenderweise gab es bei der bakteriellen Anpassung Widersprüche: positive Effekte (wie der bessere Abbau von Carbazol) gehen mit weniger wünschenswerten Ergebnissen (erhöhte Toxizität gegenüber Benzo[c]carbazol) einher. Für vier der betrachteten Verbindungen wurde ein biologischer Primärabbau festgestellt, während fünf Substanzen in keinem der Tests Anzeichen für eine mikrobielle Umsetzung zeigten, was auf ein hohes Potenzial für eine Persistenz in der Umwelt hindeutet. Die Vorhersagen softwaregestützter Modelle wurden ebenfalls mit den Messergebnissen verglichen, und es zeigte sich, dass die Modelle bei der Vorhersage der Abbaukinetik der getesteten Heterocyclen nur teilweise übereinstimmende Ergebnisse lieferten. Darüber hinaus wurde die akute Kurzzeittoxizität heterocyclischer PAK anhand von drei Arten aus verschiedenen trophischen Ebenen des aquatischen Nahrungsnetzes untersucht: Bakterien (Aliivibrio fischeri), einzellige Algen (Raphidocelis subcapitata) und Wasserflöhe (Daphnia magna). Um eine stabile Exposition aufrechtzuerhalten und Verluste, zum Beispiel durch Sorption an Gefäßwandungen, zu vermeiden, wurde die Methode des „passive dosing“ an Routinetestprotokolle angepasst. Die meisten Verbindungen wurden in diesen Tests als hochgiftig für die getesteten Organismen identifiziert, wobei festgestellt werden konnte, dass unpolare Narkose (Basistoxizität) die wahrscheinlichste Art der toxischen Wirkung der getesteten Chemikalien ist. Darüber hinaus wurden die Membran-Wasser-Verteilungskoeffizienten (KMW) der heterocyclischen PAK durch Lipidmembran-Bindungsexperimente auf festem Trägermaterial sowie mit Hilfe von Vorausberechnungen (Modellierung) bestimmt. Die gemessenen KMW-Werte stimmten eng mit den KOW-Werten überein, was darauf hindeutet, dass beide Werte gute Deskriptoren für die Vorhersage der Basistoxizität bzw. des Bioakkumulationspotenzials der getesteten heterocyclischen PAK sein können. Schließlich wurden die langfristige chronische Reproduktionstoxizität und die Bioakkumulation großer heterocyclischer PAK mit Daphnia magna als aquatischer Modellorganismus untersucht. Die „passive dosing method“ gewährleistete eine konstante Exposition selbst bei sehr niedrigen Konzentrationen (70 ng L-1 bis 68 µg L-1) in groß angelegten und komplexen Versuchssystemen. Angesichts des enormen Zeit- und Arbeitsaufwands, der für die Durchführung von Langzeit-Toxizitätstests erforderlich ist, wurde eine Methode entwickelt, um die chronische Toxizität sowie das Bioakkumulationspotenzial in einem einzigen Test zu bewerten. Alle vier getesteten Substanzen waren gegenüber Daphnia magna hochtoxisch und stark bioakkumulierend. Unerwarteterweise erholte sich die Reproduktionsfähigkeit der Daphnien jedoch schnell von den toxischen Wirkungen der Heterocyclen, wenn die Chemikalienexposition endete. Die PNECs (Predicted No Effect Concentrations) der Testsubstanzen wurden ebenfalls anhand der Daten zur chronischen Toxizität verglichen. Die Werte lagen in einer Süßwasserumgebung zwischen 1 und 150 ng L-1 (PNEC). Für die meisten Testverbindungen gibt es keine Informationen zu Monitoringdaten in der Umwelt. Die Umweltkonzentrationen heterocyclischer PAK scheinen jedoch höher zu sein als die PNEC-Werte, insbesondere an kontaminierten Standorten, was eine Gefahr für die Ökosysteme und die menschliche Gesundheit darstellt. Insgesamt tragen die Ergebnisse dieser Forschungsarbeit nicht nur zu einem umfassenderen Verständnis und zu Fortschritten bei der Bewertung der von heterocyclischen PAK ausgehenden Umweltgefahren bei, sondern liefern auch mehrere methodische Verbesserungen, die in Zukunft bei der Prüfung anderer Stoffe, die gemeinhin als 'schwierig zu testen' bezeichnet werden, angewendet werden können.

Recent research identifies a number of factors associated with public support for or opposition to environmentally-contentious energy infrastructure projects. Much of that research documents the attitudes of populations surrounding projects where energy is produced, such as powerhouses, mines, or drilling operations. I use survey and interview data to argue that those factors do not adequately reflect the concerns of landowners distributed along the 303-mile path of a rural Appalachian natural gas project, which I identify as a site of energy transmission rather than production. I use social representation theory to elicit factors unrecognized in prior research. It provides a framework for the process by which resident rural landowners become aware of, interpret, evaluate, and then respond to the Mountain Valley Pipeline. Landowners express their sense of injustice when the pipeline developer, public policymakers, and permitting authorities are unaware of or indifferent to factors that are especially relevant to them as the pipeline is imposed on their rural environment. The study is based on a sequential mixed-methods approach. I conducted a secondary analysis of the Quality of Life in Rural Virginia and West Virginia Survey dataset (Bell et al. 2019), which consists of mail surveys completed by 783 residents living in 10 counties along the route of the Mountain Valley Pipeline. In 2021 and 2022 I conducted follow-up semi-structured interviews with 25 landowners in the blast zone, which is 1,115 feet on either side of this pipeline, who had completed the survey. The first aim was to test three factors that prior research suggested are associated with attitudes toward such projects. The first factor, economic self-interest, was statistically nonsignificant for these landowners. The interview data suggest that unlike sites of energy production, where jobs stimulate support, landowners saw few jobs available for local people. Any financial value from the sale of easements did not affect their support. The second factor, political ideology, was important in other studies, because conservative ideology is associated with pro-business attitudes. In contrast, even though 60% of the landowners in this study identified themselves as conservative, there was only a weak association between political ideology and support for the pipeline, due in part to the perception of inappropriate application of eminent domain law by the pipeline developer and the courts. Distance from the pipeline, the third factor, was moderately associated with attitude toward the project, with less support for pipeline construction among landowners in the blast zone. The second aim was to use social representation theory to reveal factors in addition to distance that influenced landowners' attitudes toward the project. Interviews revealed that landowners in the blast zone were as concerned with threats to cherished water supplies, for both domestic and agricultural uses, as they were with the danger of a pipeline explosion. The interviews also revealed participants' concern for the disruption of their attachment to and dependence on their properties. These factors were underrepresented in the planning and permitting for this project. The intuitive, common-sense structure for eliciting landowners' attitudes provided by social representation theory was effective at this microscale of inquiry, and may be useful for comparative studies that further distinguish between sites of energy production and sites of energy transmission. / Doctor of Philosophy / Recent research identifies a number of factors associated with public support for or opposition to environmentally-contentious energy infrastructure projects. Much of that research documents the attitudes of populations surrounding projects where energy is produced, such as powerhouses, mines, or drilling operations. I use survey and interview data to argue that those factors do not adequately reflect the concerns of landowners distributed along the 303-mile path of a rural Appalachian natural gas project, which I identify as a site of energy transmission rather than production. I use social representation theory to elicit factors unrecognized in prior research. It provides a framework for the process by which resident rural landowners become aware of, interpret, evaluate, and then respond to the Mountain Valley Pipeline. Landowners express their sense of injustice when the pipeline developer, public policymakers, and permitting authorities are unaware of or indifferent to factors that are especially relevant to them as the pipeline is imposed on their rural environment. The study is based on a sequential mixed-methods approach. I conducted a secondary analysis of the Quality of Life in Rural Virginia and West Virginia Survey dataset (Bell et al. 2019), which consists of mail surveys completed by 783 residents living in 10 counties along the route of the Mountain Valley Pipeline. In 2021 and 2022 I conducted follow-up semi-structured interviews with 25 landowners in the blast zone, which is 1,115 feet on either side of this pipeline, who had completed the survey. Survey data suggest that factors, including economic self-gain, political ideology, and proximity to the pipeline, differ from predictions reported in prior research. Interview data suggest that in this case study those differences are associated with landowner attitudes toward danger and disruption to their sense of place. These differences may be specifically applicable to rural populations exposed to sites of energy transmission rather than sites of energy production. A recognition of these differences has important implications for project developers, public policy planners, and permitting agencies.

Radon gas may be a major air quality hazard issue inside the home. Radon (222Rn) comes from the natural breakdown of radioactive uranium (238U) via radium (226Ra) in soil, rocks, and water. Radon and its progeny contribute more than 50% of the total radiation dose to the human population due to inhalation; it can result in severe and fatal lung disease. This investigation has determined the radon concentrations in seventy-seven domestic houses in a mountainous area of Hamadan in Iran which were monitored using track-etch detectors of type CR-39 exposed for three month periods. The arithmetic mean radon concentration in Hamadan buildings was determined to be 80 Bqm-3 and also an average indoor annual effective dose equivalent for the Hamadan city population was calculated as 1.5 mSv. Maximum radon concentrations were noted during the winter and spring season. In addition to this, 28 water wells were monitored by utilizing a Sarad Doseman detector at hourly intervals over extended periods. Radon measurements were also carried out in the nearby Alisadr show cave, using Solid State Nuclear Track etch Detectors (SSNTDs) during the winter and the spring periods. In the cave, the average annual effective geometric and arithmetic mean dose for guides was 28.1 and 34.2 mSv respectively. The dose received by visitors was very low. Hamadan city is built on alluvial fan deposits which are the source of the local water supply. The data from the wells shows that the groundwater in these alluvial deposits influences the flux of radon. The atmospheric radon concentration measurement in wells above the water surface ranged from 1,000 Bqm-3 to 36,600 Bqm-3. There is evidence that radon-rich ground waters play a significant role in the transport of radon through the alluvial fan system. There is evidence that the radon concentrations in homes in Hamadan are greatly influenced by the porous nature of the underlying geology and the movement of groundwater within the alluvial fan.

Radon gas may be a major air quality hazard issue inside the home. Radon (222Rn) comes from the natural breakdown of radioactive uranium (238U) via radium (226Ra) in soil, rocks, and water. Radon and its progeny contribute more than 50% of the total radiation dose to the human population due to inhalation; it can result in severe and fatal lung disease. This investigation has determined the radon concentrations in seventy-seven domestic houses in a mountainous area of Hamadan in Iran which were monitored using track-etch detectors of type CR-39 exposed for three month periods. The arithmetic mean radon concentration in Hamadan buildings was determined to be 80 Bqm-3 and also an average indoor annual effective dose equivalent for the Hamadan city population was calculated as 1.5 mSv. Maximum radon concentrations were noted during the winter and spring season. In addition to this, 28 water wells were monitored by utilizing a Sarad Doseman detector at hourly intervals over extended periods. Radon measurements were also carried out in the nearby Alisadr show cave, using Solid State Nuclear Track etch Detectors (SSNTDs) during the winter and the spring periods. In the cave, the average annual effective geometric and arithmetic mean dose for guides was 28.1 and 34.2 mSv respectively. The dose received by visitors was very low. Hamadan city is built on alluvial fan deposits which are the source of the local water supply. The data from the wells shows that the groundwater in these alluvial deposits influences the flux of radon. The atmospheric radon concentration measurement in wells above the water surface ranged from 1,000 Bqm-3 to 36,600 Bqm-3. There is evidence that radon-rich ground waters play a significant role in the transport of radon through the alluvial fan system. There is evidence that the radon concentrations in homes in Hamadan are greatly influenced by the porous nature of the underlying geology and the movement of groundwater within the alluvial fan. / The Ministry of Health and Education; the University of Hamadan in Iran: University of Bradford: University of Kingston

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

L'ulcère de Buruli est une maladie émergente tropicale négligée. Il provoque une défiguration et une incapacité permanente pour les victimes. L'agent causal est Mycobacterium ulcerans. Cependant, le réservoir environnemental et le mode de transmission de cette bactérie ne sont pas connus. Les tentatives visant à gérer la maladie ont été freinées par le manque de connaissances concernant le mode de transmission ainsi que le réservoir environnemental de M. ulcerans. Certains écosystèmes et habitats ont été associés au risque de contracter cette mycobactérie, notamment les milieux aquatiques d'eau douce stagnants et perturbés par les activités humaines des régions tropicales. S'il n'existe pas de vecteur bien identifié, des insectes aquatiques Hémiptères sont fortement suspectés d'intervenir dans la vectorisation de cet agent infectieux à l'humain. Une compréhension complète de la distribution et du mode de transmission de la bactérie aiderait ainsi à la gestion de la maladie. Dans cette thèse, nous utilisons les outils issus de la modélisation de la niche écologique pour décrire la distribution de M. ulcerans. Suite à la construction d'un modèle au Cameroun, en Afrique Centrale, et testé avec une seconde base de données en Guyane Française (Amérique du Sud), nous trouvons que l'agent pathogène montre des variations saisonnières notables dans la répartition de nos sites d'étude, au Cameroun. Pendant la saison humide, M. ulcerans est plus fréquente dans les grands bassins versants et en absence de marécages, tandis que durant la saison sèche, la bactérie est plus présente dans les petits bassins versants où peuvent être présents dans les zones marécageuses. Notre étude a permis de générer des cartes de répartition de l'agent pathogène dans la région d'étude, qui pourront être utilisées dans des études ultérieures contribuant à mieux gérer le risque infectieux pour cette maladie. De plus, nous avons développé une modélisation des niches écologiques des insectes aquatiques soupçonnés d'être des vecteurs de l'agent pathogène. Basé sur un protocole d'échantillonnage d'insectes aquatiques qui couvre l'ensemble du Cameroun, nous avons construit un modèle suivant la méthode de l'entropie maximale. Ceci nous a permis d'interpoler notre modèle sur toute l'Afrique de l'Ouest. Nous avons ensuite testé une corrélation entre la répartition prévue des insectes potentiellement vecteurs, et la prévalence de l'ulcère de Buruli. Nous mettons en évidence une corrélation positive significative entre la répartition des insectes et la répartition de la maladie, et trouvons que cette corrélation varie significativement dans l'espace et le temps. Ceci est cohérent avec la possibilité d'une transmission multi-hôte pour cet agent pathogène.Enfin, en collaboration avec d'autres auteurs, nous avons pu explorer différents facteurs influençant la distribution de M. ulcerans, tels que les réseaux et la structure de la communauté biotique, ou encore l'impact de l'occupation du sol sur la distribution de l'ulcère de Buruli dans notre région d'étude d'Akonolinga au Cameroun. Et enfin nous avons testé le changement de distribution de la maladie à une plus grande échelle, entre le Bénin et le Nigeria. Cette thèse contribue à une meilleure compréhension de la distribution de Mycobacterium ulcerans et de l'ulcère de Buruli, fournissant des éléments de preuve d'une transmission multi-hôtes de la mycobactérie, ainsi que les premières cartes de répartition de l'agent pathogène pour la région d'Akonolinga au Cameroun. / The Buruli ulcer is an emerging environmentally acquired infectious neglected tropical disease. It causes permanent disability and disfigurement in victims. The causative agent is Mycobacterium ulcerans; however the environmental reservoir and mode of transmission of this bacterium are not known. Attempts to manage the disease have been hampered by lack of knowledge of the mode of transmission and the environmental reservoir of M. ulcerans. Certain environments have been associated with the disease, notably disturbed aquatic environments composed of small bodies of stagnant water. There is no known vector, though aquatic insects have been implicated as possible vectors. A full understanding of the distribution and mode of transmission of the bacterium would help in management of the disease.In this thesis, we use the tools developed in ecological niche modelling to describe the distribution of M. ulcerans. Following the construction of a model in Cameroon, Central Africa, and tested against a second database in French Guiana (South America), the pathogen is found to have notable seasonal changes in its distribution in our study sites in Cameroon. In the wet season, M. ulcerans is more common in large watersheds, while in the dry season the bacterium is more common in small watersheds. This enabled the generation of hazard maps of the pathogen distribution in the study region, which will be used in future studies and management of the disease. Following this we undertook ecological niche modelling to describe the distribution of the aquatic insects suspected to be vectors of M. ulcerans. Based on a sampling protocol that spanned the country of Cameroon, we undertake maximum entropy modelling, which enabled us to interpolate our model across all of West Africa. With these maps we explore the correlation between the predicted distribution of the insects to the prevalence of the Buruli ulcer. We find a significant positive correlation between the distribution of the insects and the distribution of the disease, and find that this correlation undergoes significant changes in space and time, consistent with the model of multi-vectorial transmission of the disease.Finally, in collaboration with other authors, we have assisted in exploring how the distribution of M. ulcerans changes according to community structure networks, how the distribution of the Buruli ulcer disease changes in our study region of Akonolinga, Cameroon, and how the distribution of the disease changes at a larger scale, between Benin and Nigeria. This thesis contributes to our understanding of the distribution and drivers of Mycobacterium ulcerans and the Buruli ulcer, providing evidence of multi-vectorial transmission of the disease, and the first hazard maps of the pathogen for Akonolinga, Cameroon.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The coastal landscape presents one of the most complex systems due to the convergence of atmospheric, continental and oceanic agents. Under this fragile and dynamic biophysical composition, anthropic systems, which are manifested in the most diverse types of use and occupation, are spatialized. Associated with such conjuncture, we highlight the coastal landscape of the municipality of Aracaju, central coast and capital of Sergipe state, which is the object of study of this thesis. The occupation of this area, intensified after the 70’s, is a result of the urban expansion of the city towards the coastal front. This process has been notably led by the joint action between private capital and state action and assumed the shape of a predatory model whose implication is the continuous suppression of natural features and the interruption of geoecological functions performed by them. In view of the problem that has been exposed, the scope of this research study has been to evaluate the risks associated with the coastal landscape of Aracaju, based on the postulates of Geoecology. The method adopted in order to comprehend the object of study was the systemic approach, which comprehends a holistic analysis of landscape components. The risk assessment included: the analysis of the coastal front occupation – responsible for evidencing phases, settlement patterns and, mainly, indicating the agents that have influenced this process; the geoecological study of the landscape – in which we analyzed the composition, the structure, the evolution and the function exerted by the delimited units (Marine Terrace, Tidal Flat, Dune Field and Recent Sedimentation Environments), such as the environmental condition of the landscape and the biophysical vulnerability of the units; and, ultimately, the delimitation of risk areas – assessed by the interpolation of hazard indicators (magnitude and susceptibility) and by the vulnerability of anthropic structures. What has been concluded in the space of this thesis is that the environmental risk scenarios emerged from the combination of the high natural susceptibility of geoecological units and the reduction of resistance and resilience of physical components in the face of the analyzed hazards – intense rainfall events and coastal erosion. This limitation of support capacity comes from a pattern of urban expansion that has not made the maintenance of balance between elements of the landscape feasible. As the occupation process itself has occurred in a disordered way, anthropic structures are deficient and unable to completely absorb the effects of hazardous events, a fact which accentuates vulnerability. The result of this conjunction is that much of the area investigated is framed in the medium and high risk degrees, with emphasis on the Marine Terrace, especially when associated with wet shoals and lagoons, and the Deposits Associated with Coalescence of Sand Banks. In an analysis of future scenarios, based on the evaluation of historical-current tendencies, it is deduced that in the face of the continuity of the assessed process, there is an evident propensity for both the increase and the aggravation of risk scenarios. / A paisagem costeira constitui-se como um dos sistemas mais complexos em razão da convergência dos agentes atmosféricos, continentais e oceânicos. Sob essa composição biofísica frágil e dinâmica espacializam-se os sistemas antrópicos, manifestos nos mais diversos tipos de uso e ocupação. Associada a essa conjuntura destaca-se a paisagem costeira do município de Aracaju, litoral central e capital do estado de Sergipe, objeto de estudo da presente tese. A ocupação dessa área, intensificada no pós-década de 70, é decorrente da expansão urbana da cidade em direção à frente litorânea. Tal processo, conduzido notadamente pela ação conjunta entre capital privado e ação estatal, tem assumido contornos de um modelo predatório cuja implicação é a contínua supressão das feições naturais e interrupção das funções geoecológicas desempenhadas por estas. Diante da problemática exposta esta pesquisa teve por escopo avaliar os riscos associados à paisagem costeira do município de Aracaju alicerçada nos postulados da Geoecologia. O método adotado para compreensão do objeto de estudo foi a abordagem sistêmica, que pressupõe uma análise holística dos componentes da paisagem. A avaliação do risco englobou: a análise da ocupação da frente litorânea – responsável por evidenciar as fases, os padrões de assentamento e, sobretudo, indicar os agentes que influenciaram nesse processo; a avaliação geoecológica da paisagem – em que foram analisadas a composição, a estruturação, a evolução e a função exercida pelas unidades delimitadas (Terraço Marinho, Planície de Maré, Campo de Dunas e Ambientes de Sedimentação Recente), tal como o estado ambiental da paisagem e a vulnerabilidade biofísica das unidades; e, por fim, a delimitação das áreas de risco – mensurada a partir da interpolação dos indicadores de perigo (magnitude e suscetibilidade) e da vulnerabilidade das estruturas antrópicas. O que se conclui no âmbito desta tese é que os cenários de risco ambiental são produtos da combinação entre a elevada suscetibilidade natural das unidades geoecológicas e a redução da capacidade de resistência e resiliência dos componentes físicos diante dos perigos analisados – eventos pluviométricos intensos e erosão costeira. Esta limitação da capacidade de suporte provém de um padrão de expansão urbana que tem inviabilizado a manutenção de equilíbrio entre os elementos da paisagem. Como o próprio processo de ocupação ocorreu de forma desordenada, as estruturas antrópicas são deficitárias e não são capazes de absorver completamente os efeitos dos eventos perigosos, fato que acentua a vulnerabilidade. O resultado desta conjunção é que grande parte da área investigada está enquadrada nos graus mediano e elevado de risco, com destaque para o Terraço Marinho, principalmente quando associados aos baixios úmidos e lagoas, e os Depósitos Associados à Coalescência de Bancos Arenosos. Em uma análise dos cenários futuros, baseado na avaliação das tendências histórico-atuais, deduz-se que mediante a continuidade do processo aferido, há propensão evidente tanto da potencialização, quanto do agravamento dos cenários de risco.