Analysis of seaweed as a vector for microplastics is an integral part of understanding the formation and deposition of micro-sized plastic waste in seawater. The project itself originated due to the influx of seaweed (and mismanaged plastic waste) residing on the shores of St. Kitts and Nevis and the constant deposition of plastic pollution intertwined within the seaweed. The natural occurrence of the two together lead to the consideration of fragmented plastics remaining on the seaweed. The objective of this research is to stain, identify, and quantify the concentration of microplastics sourced from both store-bought and environmental seaweed samples. A Nile red solution dissolved in either acetone or methanol was used to stain the microplastics, as per a proven method. The fluorescence of the stained microplastics was measured (excitation: 523-543 nm and emission: 580-640 nm) to identify potential dissolution. The seaweed was washed of microplastics and the solid particles collected were evaluated using infrared (IR) spectroscopy. The fluorescence and infrared spectrum results were compared to spectra within the Spectral data base system (SDBS) for the most common plastics: polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polypropylene (PP), polycarbonate (PC). The use of a fluorescence microscope allowed for direct quantification of microplastics over a specific area of the sample and therefore allowed for further identification of microplastic presence.

The environmental mobility of Technetium-99 is inextricably tied to its oxidation state. Under oxidizing conditions Tc-99 predominates as the Tc(VII)O4- anion. This anion has a high solubility and is precluded from sorption on most soil or mineral surfaces, giving it a high environmental mobility. Under reducing conditions, Tc-99 predominates as Tc(IV)O2 or Tc(IV)2S7. Tc(IV) species tend to be insoluble and are therefore immobile. Due to this redox dichotomy, there has been significant interest in developing reductive immobilization strategies for Tc-99, particularly in anoxic environments where Tc(IV) is conventionally assumed to be stable. However, O2 is not the only common environmental oxidant. Many high valent manganese species are environmentally prolific and well known to exist in anoxic and overall reducing environments. These powerful oxidants can create localized oxidizing conditions in otherwise reducing environments. Limited research on the oxidation of Tc(IV) species has left a knowledge gap in the true recalcitrance of such immobilization forms in environmental settings. Our work aims to bridge this knowledge gap by studying the oxidation of Tc(IV) by various, environmentally common, high valent manganese species. Mn(III)-ligand complexes in particular have been overlooked. Up until recently, aqueous Mn(III) was assumed to be absent from the environment due to its disproportionation in aqueous systems without suitable complexing ligands. More recently, Mn(III)-ligand complexes have been shown to be prolific in a variety of natural waters. We have shown that various manganese oxides and Mn(III)-ligand complexes are capable of rapidly oxidizing Tc(IV) to Tc(VII), even in the absence of oxygen, resulting in dissolution of Tc-99 and release to the aqueous phase. This thesis presents novel information on the redox interface chemistry of Tc-99, which is crucial to developing effective remediation methods.

Neste trabalho buscaram-se formas de aumentar a eficiência do processo de ozonização sobre a degradação/mineralização de corantes empregados pela indústria têxtil, especificamente do azocorante Preto Remazol B, avaliando o emprego do processo de ozonização catalítica tanto homogênea quanto heterogênea. O ozônio mostrou uma grande eficiência para promover a degradação dos três tipos de corantes estudados (azo, antraquinona e ftalocianina); permitindo que soluções destes corantes com concentração de 100 mg L-1 sofressem uma total descoloração (destruição do grupo cromóforo) em menos de 2 minutos de ozonização. Em meio ácido, o ozônio tende a reagir via o mecanismo direto e devido a isto a redução no teor de carbono orgânico total (COT) dos poluentes costuma ser menos eficiente. Em 30 minutos de tratamento o processo O3/pH3 permitiu somente 30% de mineralização do azocorante estudado. Por outro lado, o O3 pode ter sua decomposição catalisada por vários materiais, levando à formação de espécies radicalares, principalmente o radical hidroxila (HO.). Devido ao caráter não seletivo dos radicais hidroxila, o mecanismo de ozonização indireto costuma ser mais eficiente na oxidação de compostos orgânicos. Um exemplo clássico deste mecanismo é o processo O3/pH11, que mineralizou 56% do COT do azocorante após 30 minutos de ozonização. Uma estratégia para promover uma melhora na mineralização do corante Preto Remazol B pelo processo de ozonização em meio ácido foi a adição de peróxido de hidrogênio ao meio reacional. O tratamento O3/pH3/H2O2 permitiu um aumento de 51% na mineralização do azocorante após 30 minutos de ozonização. O aumento da eficiência do ozônio também foi avaliado empregando-se o processo de ozonização na presença de metais (Mn2+e Fe3+). Em 30 minutos de tratamento, o processo O3/pH3/Mn2+ mineralizou 67, 78 e 57% do COT dos corantes Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. No mesmo tempo de tratamento O3/pH3/Fe3+ permitiu uma remoção de COT de 57, 64 e 41% para Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. A presença dos metais estudados na forma sólida (MnO2) ou em suportes (SiO2/MnO2 e SiO2/Fe2O3), além de permitir uma remoção de até 79% do COT do azocorante em 30 minutos de tratamento, também mostra uma alternativa para viabilizar o emprego dos agentes catalisadores da decomposição do ozônio, uma vez que na forma suportada os mesmos podem ser utilizados de forma contínua, minimizando etapas de recuperação ou perdas destes materiais. / The main goal of this study was to find means to increase the efficiency of ozonation process over the degradation/mineralization of dyes used in the textile industry, mainly the azodye Remazol Black B, evaluating the use of either homogeneous or heterogeneous catalytic ozonation methods. Ozone showed great efficiency to promote the degradation of the three types of studied dyes (azo, anthraquinone and phtalocyanine) enabling the discoloration (destruction of chromophore group) of solutions with 100 mgdye L-1 in less than 2 minutes. In acidic medium, ozone tends to react via the direct mechanism. In this way, the reduction of total organic carbon (TOC) of the polluents uses to be less efficient. In 30 minutes of treatment, the process O3/pH3 allowed only 30% of mineralization of the studied azodye. On the other hand, O3 can be decomposed by several materials, leading to the formation of radical species, mainly the hydroxyl radical (HO.). Due to the nonselective character of hydroxyl radicals, the indirect mechanism of ozonation usually is more efficient in the oxidation of organic compounds. A classic example of this mechanism is the process O3/pH11 that mineralized 56% of TOC of the azodye after 30 minutes of ozonation. Another strategy to promote an improvement in the mineralization of the azodye Remazol Black B using the ozonation process in acid medium was the addition of hydrogen peroxide to the reactional medium. The treatment O3/pH3/H2O2 enabled an increase of 51% in the mineralization of the azodye after 30 minutes. The increase in the efficiency of ozone was also evaluated using the ozonation process in the presence of metallic ions (Mn2+ and Fe3+). In 30 minutes of treatment, the process O3/pH3/Mn2+ mineralized 67, 78 and 57% of the TOC of the dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. In the same time of treatment, the process O3/pH3/Fe3+ mineralized 57, 64 and 41% of the TOC of he dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. The presence of the studied metals in the solid form (MnO2) or on supports (SiO2/MnO2 e SiO2/Fe2O3), enabled the removal of up to 79% of the TOC of the azo in 30 minutes of ozonation. Moreover, these methods showed an alternative to permit the use of catalytic agents to decompose ozone, as in the supported form, they can be used in a continuous form, minimizing steps of recuperation or loss of these materials.

<p>The aim of the study was to investigate if methane emission in a constructed wetland changed in a diurnal pattern correlating to temperature, humidity or light conditions. The gas measurements were carried out with a static chamber technique. The wetland (in Nykvarn outside of Linköping, Sweden) takes care of wastewater to reduce the nitrogen loads. Measurements were carried out at three different occasions in the summer of 1998 on two sites in the wetland. One site was close to the inflow, inhabited by Lemnaceae, and another site was located further downstream inhabited by the emergent macrophyte Typha latifolia. The results showed a variation, but no discernible diurnal pattern. The Typha site had a methane emission rate of 166 mg CH₄ m-2d-1 and the Lemnaceae site had an methane emission rate of 712 mg CH₄ m-2d-1. In all experiments at the Typha site, the highest methane emission rate was obtained at sunrise.</p>

<p>Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. </p><p>In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings.</p><p>To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of >95% for all monoterpenes and formed products included in the investigation.</p><p>Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆³-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation.</p><p>Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene. </p>

<p>Phosphorus (P) is often the limiting nutrient in lacustrine and brackish eco-systems, and enhanced input of P into an aquatic system might therefore negatively impact the environment. Because modern waste water manage-ment have reduced external P input to surface waters, internal P loading from the sediment has become one of the main P sources to aquatic ecosys-tems, in which relatively unknown organic P compounds seem to be more active in P recycling than previously thought.</p><p>This thesis focus is on improving analysis methods for organic P com-pounds in lacustrine and brackish sediments, as well as determining which of these compounds might be degraded, mobilized and subsequently recycled to the water column and on what temporal scale this occur. In both lacustrine and brackish environments, the most labile P compound was pyrophosphate, followed by different phosphate diesters. Phosphate monoesters were the least labile organic P compounds and degraded the slowest with sediment depth. In regulated lakes, it was shown that pyrophosphate and polyphos-phate compound groups were most related to lake trophic status, thus indi-cating their involvement in P cycling. This thesis also indicates faster P turn-over in sediment from the brackish environment compared to sediment from the lacustrine environment. </p><p>A comparison of organic P extraction procedures showed that pre-extraction with EDTA, and NaOH as main extractant, was most efficient for total P extraction. Using buffered sodium dithionite (BD) as a pre-extractant and NaOH as main extractant was most efficient for extracting the presuma-bly most labile organic P compound groups, pyrophosphate and polyphos-phate. Furthermore, it was determined that organic P compounds associated with humic substances were more recalcitrant than other P compounds, that the BD step used in traditional P fractionation might extract phosphate monoesters, and that NMR is a statistically valid method for quantification of organic P compounds in sediment extracts.</p>

Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings. To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of &gt;95% for all monoterpenes and formed products included in the investigation. Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆3-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation. Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene.

The aim of the study was to investigate if methane emission in a constructed wetland changed in a diurnal pattern correlating to temperature, humidity or light conditions. The gas measurements were carried out with a static chamber technique. The wetland (in Nykvarn outside of Linköping, Sweden) takes care of wastewater to reduce the nitrogen loads. Measurements were carried out at three different occasions in the summer of 1998 on two sites in the wetland. One site was close to the inflow, inhabited by Lemnaceae, and another site was located further downstream inhabited by the emergent macrophyte Typha latifolia. The results showed a variation, but no discernible diurnal pattern. The Typha site had a methane emission rate of 166 mg CH4 m-2d-1 and the Lemnaceae site had an methane emission rate of 712 mg CH4 m-2d-1. In all experiments at the Typha site, the highest methane emission rate was obtained at sunrise.

Phosphorus (P) is often the limiting nutrient in lacustrine and brackish eco-systems, and enhanced input of P into an aquatic system might therefore negatively impact the environment. Because modern waste water manage-ment have reduced external P input to surface waters, internal P loading from the sediment has become one of the main P sources to aquatic ecosys-tems, in which relatively unknown organic P compounds seem to be more active in P recycling than previously thought. This thesis focus is on improving analysis methods for organic P com-pounds in lacustrine and brackish sediments, as well as determining which of these compounds might be degraded, mobilized and subsequently recycled to the water column and on what temporal scale this occur. In both lacustrine and brackish environments, the most labile P compound was pyrophosphate, followed by different phosphate diesters. Phosphate monoesters were the least labile organic P compounds and degraded the slowest with sediment depth. In regulated lakes, it was shown that pyrophosphate and polyphos-phate compound groups were most related to lake trophic status, thus indi-cating their involvement in P cycling. This thesis also indicates faster P turn-over in sediment from the brackish environment compared to sediment from the lacustrine environment. A comparison of organic P extraction procedures showed that pre-extraction with EDTA, and NaOH as main extractant, was most efficient for total P extraction. Using buffered sodium dithionite (BD) as a pre-extractant and NaOH as main extractant was most efficient for extracting the presuma-bly most labile organic P compound groups, pyrophosphate and polyphos-phate. Furthermore, it was determined that organic P compounds associated with humic substances were more recalcitrant than other P compounds, that the BD step used in traditional P fractionation might extract phosphate monoesters, and that NMR is a statistically valid method for quantification of organic P compounds in sediment extracts.

<p>Paper spray mass spectrometry (PS-MS) is an ambient ionization technique that has been proven useful in many types of investigative analyses. However, the use of this technique with regards to environmental samples has been largely unexplored since the technique’s development. In this work, paper spray mass spectrometry was utilized to detect and quantify compounds for environmental, forensic and chemical defense applications. Due to the sensitive nature of some projects, the work was split into two volumes. Volume 1 focuses on the detection of pharmaceuticals in soil using paper spray (Chapter 2) and the detection of chemical warfare agent (CWA) simulants and CWA hydrolysis products (Chapter 3). Volume 2 focuses on the detection and quantitation of fentanyl analogs in environmental matrices. Chapter 5 focuses on the rapid analysis of fentanyl analogs in soil matrices. The following chapter evaluates the ability of PS-MS to detect low concentrations of fentanyl analogs in water (Chapter 6). Throughout this work, paper spray has proven to be an effective, rapid alternative to chromatography for the analysis of environmental samples. </p>