This research involved the study of sediment cores from Loch Etive, Loch Long, Loch Goil and Loch Fyne with the aims of investigating the geochemistry of natural, and manmade radionuclides and heavy metals within the sea loch environment. The main aims of the research were to determine accumulation rates and the extent of mixing within these sediments and to assess the fluxes, sources and temporal variations in input of pollutant heavy metals to these environments. In recent years it has been suggested that Pb is mobile in sea loch sediments which questions the validity of applying ²¹⁰Pb dating in this environment. This has important implications with respect to interpreting sediment cores to assess temporal trends of pollutant inputs and investigating the rates of physical and biogeochemical processes that are taking place in the coastal environment. Hence, one of the aims of this research was to determine whether Pb was mobile in these sediments. The ²⁰⁶Pb/²⁰⁷Pb isotope ratio can potentially be used to determine the extent of pollutant Pb input from leaded petrol to the environment and a further objective of the work was to investigate the isotopic signature of pollutant Pb in the sediment. Concentration of ²¹⁰Pb, ²²⁶Ra, ²²⁸Ra, ²²⁸Th, ²³⁸U, ¹³⁷Cs, ¹³⁴Cs and ²⁴¹Am in the sediments were analysed using gamm a spectroscopy and the heavy metals, Pb, Zn and Cu were determined using X-ray Fluorescence. Stable Pb isotope ratios were determined using Inductively coupled plasma Mass spectrometry. The results obtained indicated that Pb is not subject to diagenetic mobility in these sediments and that ²¹⁰Pb profiles can be used to determine sedimentation rates for most of the sediment cores. lt was not possible to determine accumulation rates for the two cores from Loch Fyne by ²¹⁰Pb dating, and in this case the sedimentation rate was assessed by correlating the maximum concentration of ¹³⁷Cs in the sediments with the maximum ¹³⁷Cs discharge from Sellafield, BNFL's reprocessing plant located on the Cumbrian coast. The flux of ²¹⁰Pb to the lochs varied significantly suggesting that there has been sediment focusing of fine and/or organic rich material to the deeper sites, resulting in an enhanced flux of ²¹⁰Pb to these sediments. Sellafield waste radionuclides also provided useful chronologies by relating sediment maximum concentrations to maxima in the discharges. ¹³⁷Cs was observed to be subject to diffusive movement, invalidating the use of its total depth of penetration as a chronological indicator. The temporal trends of pollutant metal input agreed well with known historical trends and the Pb isotope profiles indicated that the onset of deposition from pollutant Pb from petrol occurred in the late 1920's. The maximum input of Pb from petrol peaked in the early 1980's and since then there has been a decrease in this input. The two sea lochs which were closest to the industrial centre of Glasgow exhibited a large anthropogenic pollutant input, confirming that these sediments have been highly perturbed by human activities, either directly as a result of sludge dumping or due to changes in land use (eg. road construction, deforestation, etc.) in the catchment. All the sea lochs reflected a change in the supply of material to the sediments over the last eighty years, indicating that increased anthropogenic activity has had an effect on these environments.

The goal of this work was to establish the suitable and limiting concentrations of Zn, Cu and Mn compounds during syngas fermentation. The results showed that cells encased in polyvinylidene difluoride (PVDF) membranes had a faster accumulation of methane in reactors containing fermentation medium dosed with 5 mg/L of each heavy metal compared to free cells. It was also revealed that total inhibition of biohydrogen production occurred in medium containing 5 mg/L Cu, 30 mg/L Zn and 140 mg/L Mn while the most suitable metal concentration level was 0.1 mg/L Cu, 0.6 mg/L and 2.8 mg/L Mn. In addition, a comparison test showed that for the most suitable metal concentration in the medium, rate of performance at pH 6 and 7 was higher than at pH 5.

published_or_final_version / Chemistry / Master / Master of Philosophy

Urbanisation leads to increases in stormwater runoff, resulting in elevated contaminant (e.g. metal, sediment, and nutrient pollutant) loads, decreased local infiltration and greater peak flow intensities. Heavy metal contaminants of concern, primarily copper (Cu), lead (Pb), and zinc (Zn), originate from a variety of sources including wear-and-tear of vehicle parts, corrosion of alloy roofs, legacy petroleum contamination, and multifarious construction practices. Different technologies have been used to mitigate stormwater runoff, ranging from traditional drainage networks fitted with concrete proprietary devices (e.g. vortex sediment separators and filters) to more environmentally integrated sustainable solutions. Rain gardens, a type of Sustainable Urban Drainage System (SUDS) or Water Sensitive Urban Design (WSUD), are employed to control stormwater peak flows and runoff volumes and simultaneously reduce contaminant loads to neighbouring waterways through biologically-active landscaped design. Despite increases in use of rain gardens as a best management practice (BMP) to treat urban stormwater runoff, there is a dearth of knowledge about their treatment and infiltration performance worldwide. It is believed that incorporating topsoil into rain garden design is likely to improve contaminant removal efficiencies (Davis et al. 2001; ARC 2003; Fletcher et al. 2004; Carpenter and Hallam 2010), but design recommendations are not informed by performance data which is limiting. Performance data is necessary for understanding the long-term responses of bioinfiltrative treatment systems and for modelling efforts aiming to predict their mitigation behaviour (Fletcher et al. 2004). In order to evaluate the influence of substrate composition on stormwater treatment and hydraulic effectiveness in rain gardens, mesocosm-scale (180 L, 0.17 m2) laboratory systems were established. Saturated (constant-head) hydraulic conductivity was determined before and after contaminant (Cu, Zn, Pb and nutrients) removal experiments on three rain garden systems comprising various proportions of organic topsoil. Raw stormwater runoff from a neighbouring Christchurch city catchment was collected, characterised, and applied in the removal efficiency experiments. The system with only topsoil had the lowest saturated hydraulic conductivity (160 mm/hr initial to 164 mm/hr final) and poorest metal (Cu, Zn) removal efficiency (Cu 0.3%, Zn 60.5% and Pb 89.5%) at a ‘standard’ contaminant loading rate (Cu = 5.99 ± 0.73 µg/min, Zn = 57.89 ± 6.06 µg/min, Pb = 13.65 ± 2.80 µg/min). The sand-only system demonstrated good metal removal (Cu 56.4%, Zn 73.5%, and Pb 81.6%) with hydraulic conductivity (up to 805 mm/hr) adequate for practical implementation (i.e. greater than the 13 mm/hr minimum requirement (ARC 2003; MDE 2009; SFPUC 2009)). Overall, total metal amounts in the effluent were <50% of influent loads for all experiments, with the exception of Cu in the topsoil-only system, whose removal was negligible (0.3%). Greater metal removal was observed when effluent pH was elevated (up to pH 7.38). The pH increase (from an initial pH of 6.23 in raw stormwater) was provided by the calcareous sand, whereas the topsoil-only system lacked an alkaline source. Consequently, organic topsoil had poorer contaminant removal due to higher dissolved metal fractions, which are more difficult to immobilise at the lower pH. The relationship between pH and dissolved fraction was highly significant (Pearson’s Correlation, p < 0.0001, df = 74) for Cu, Zn, and Pb. Mesocosm-scale systems were then re-established with a calcareous substrate supplement to quantify the effects of pH augmentation on contaminant removal and hydraulic efficiencies. Mussel shells, a waste product from the shell-fish industry, were employed in two different volumetric proportions. Metal removal efficiency was increased in systems with mussel shells (Cu up to 46.6%, Zn up to 80.2%, Pb up to 88.7%) compared to the topsoil-only system (Cu 27.5%, Zn 55.5%, Pb 81.0%). Larger increases in removal efficiency were seen for Cu and Zn because increases in pH from mussel shell enhanced particulate fractions, which are easier to remove in filtration systems, while Pb is mainly in the particulate form at influent pH (Morrison et al. 1990). Effluent from systems with mussel shells also had higher hardness (hardness up to 101.7 mg/L as CaCO3) compared with 22.4 mg/L as CaCO3 in topsoil-only effluent. Hardness reduces metal ecotoxicity (Hyne et al. 2005). Results of these experiments show that mussel shells are a promising rain garden substrate capable of increasing metal removal efficiency and also decreasing metal ecotoxicity in effluent of bioinfiltration systems. Concurrently, an operational field-scale “rain garden” (42 m3; 60 m2) in Christchurch was monitored for hydraulic throughput and contaminant removal. The field system performed extremely well at mitigating peak flows, detaining water throughout storm events and removing total suspended solids (TSS) (90.6% average removal). However, the system failed to reduce effluent median total metal concentrations (Cu = 15.9 µg/L, Zn = 139.6 µg/L, Pb = 11.7 µg/L) below relevant ANZECC guidelines (Cu = 1.8 µg/L, Zn = 15.0 µg/L, Pb = 5.6 µg/L) highlighting the opportunity to optimise these field designs to improve metal removal.

The aim of this study was to develop a suitable monitoring protocol for mediated amperometric whole-cell biosensors for in situ assessment of heavy metals in soil. E. coli 8277, Pseudomonas 9773, Pseudomonas 9046 and Pseudomonas 8917 were screened as biosensor catalysts to select the sensitive biosensor configurations to heavy metals. A new protocol was developed for monitoring heavy metals in defined solution, soil pore water, and in situ in soil. This study also demonstrated the applications of mediated amperometric bacterial biosensors for in situ assessing the bioavailability and toxicity of heavy metals in freshly spiked soils or historically contaminated soils, and mixture toxicities of heavy metals. It was found that the biosensors incorporating selected bacterial strains were appropriately sensitive to copper, but less sensitive to Zn, Pb, and Hg, compared to Microtox assay. The advantage of the mediated amperometric bacterial biosensor system is its in situ application in soils. The present study demonstrated that soil pore water does not accurately reflect conditions of soil ecosystem, and that in situ bioassays are more reliable for determining the bioavailability and toxicity of heavy metals. This is the first reported use of disposable whole cell biosensors for in situ heavy metal bioavailability and toxicity assessment. The biosensor protocol developed here can be adapted to allow the incorporation of dfferent bacterial biocatalysts for applications in soil quality assessment, screening of sites for contamination ‘hot spots’, and the evaluation of soil degradation or rehabilitation from metal pollution. Mediated amperometric bacterial biosensors are not analyte specific, their response reflecting the metabolic impact of the combined chemical and physical properties of the environment to which they are exposed. In assessing the toxicity of soil samples from fields using these biosensors, it is vital to get appropriate control soil samples. The conditions of soil samples also need to be well defined. The sensitivity of the mediated amperometric whole-cell biosensors to heavy metals need to be further improved. Investigations are also required to determine how the natural conditions affect the application of the biosensor system in the field.

No description available.

Summary: This thesis is focused on mapping of contaminants released into the environment probably due to uranium mining. These chemical contaminants are used to reconstruct the sedimentary processes. In the thesis we evaluate geochemical situation in the catchment area in the locality Borecek (part of the municipality Ralsko) using the overbank sediments as sedimentary archives of pollution during the last decades by elements U, Ba, Zn, Ni and 226 Ra. A map of aerial survey of gamma activity was used to select the area of interest, for more accurate localisation we used a surface gamma spectrometry. On Borecek we retrieved ten depth profiles of alluvial sediments (up to 230 cm) and one in Mimon, all samples were subjected to X-ray fluorescence spectral analysis (XRF), across the floodplain we performed gamma wire logs. For interpretations of floodplains architecture electrical resistivity tomography (ERT) was used and selected profiles were analysed for the activity of 226 Ra and 210 Pb. Interrelation of 226 Ra and Ba proved that radiobarite is the main source of the gamma activity. 210 Pb / 226 Ra ratio was used as sediment age indicator. With enrichment factor (LEF), we performed chemostratigraphic correlation of the sediments, for that the concentration of the target elements is corrected for varying...

Summary: This thesis is focused on mapping of contaminants released into the environment probably due to uranium mining. These chemical contaminants are used to reconstruct the sedimentary processes. The aim of the thesis was both the geochemical assessment of the situation in the catchment area of the Ploucnice River in Boreček using the flood sediments from the research points as sedimentary archives pollution for last decades. With depth profiles, gamma wire log, XRF and enrichment factors (LEF), we have tried to perform chemostratigraphic correlation of the sediments. As target elements U, Ba, Zn and Ni were chosen, whose concentrations are related to the grain size of the sediment. Furthermore, the theory of secondary pollution is developed.

M.Sc. / Please refer to full text to view abstract

Orientador: Eliana Gertrudes de Lemos / Coorientador: Cristiane Moretto / Banca: Paulo Inácio da Costa / Banca: João Martins Pizauro Junior / Resumo: Nas últimas décadas, a síntese microbiana de biopolímeros com propriedades biotecnológicas tem atraído atenção crescente. Este trabalho relatou o efeito dos íons metálicos cobre bivalente (Cu2+) e cromo hexavalente (Cr6+) na biossíntese de exopolissacarídeo (EPS) e polihidroxibutirato (PHB), produzidos pela bactéria Rhizobium tropici (LBMP-C01). No ensaio de concentração mínima inibitória (CMI), a rizobactéria apresentou sensibilidade às concentrações superiores a 0,1 mmol L-1 para Cu2+ e 0,05 mmol L-1 para o íon Cr6+. O estudo do efeito destas concentrações de íons metálicos sobre a produção de EPS e PHB, este foi cultivado em meios PSYlíq sem a presença dos íons (controle) e suplementados com os íons separadamente (Cu2+ e Cr6+) e em mistura (Cu2+ + Cr6+). A curva de cultivo mostrou diferenças significativas entre o meio PSYlíq controle e os demais tratamentos contendo os íons metálicos nas concentrações avaliadas. Apesar do efeito dos íons metálicos no cultivo, todos os tratamentos apresentaram células viáveis. Quanto à ação dos íons metálicos sobre a produção de EPS e PHB, foi observado que os tratamentos contendo o íon cromo e os íons em mistura (Cu2+ + Cr6+) reduziram a produção de ambos os biopolímeros. No entanto, o tratamento suplementado com somente o íon Cu2+ induziu o aumento da produção de até 48% de EPS e 46,66% de PHB em relação ao controle, após 144 horas. O estudo de FTIR indicou mínimas diferenças nos grupos funcionais presentes nas moléculas dos biopolímeros... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In the last decades, the microbial synthesis of biopolymers with biotechnological properties has attracted increasing attention. This work reported the effect of bivalent copper (Cu2+) and hexavalent chromium (Cr6+) ions on exopolysaccharide biosynthesis (EPS) and polyhydroxybutyrate (PHB), produced by the bacterium Rhizobium tropici (LBMP-C01). In the minimum inhibitory concentration (MIC) test, rhizobacteria showed sensitivity to concentrations higher than 0.1 mmol L-1 for Cu2+ and 0.05 mmol L-1 for the Cr6+ ion. The study of the effect of these metal ion concentrations on EPS and PHB production was carried out in PSYlíq media without the presence of ions (control) and supplemented with ions separately (Cu2+ and Cr6+) and in a mixture (Cu2+ Cr6+). The culture curve showed significant differences between the control PSYlíq medium and the other treatments containing the metal ions at the concentrations evaluated. Despite the effect of metal ions on the culture, all treatments had viable cells. As for the action of the metal ions on the production of EPS and PHB, it was observed that the treatments containing the chromium ion and the ions in the mixture (Cu2+ + Cr6+) reduced the production of both biopolymers. However, the treatment supplemented with Cu2+ alone induced an increase in the production of up to 48% of EPS and 46.66% of PHB in relation to the control after 144 hours. The FTIR study indicated minimal differences in the functional groups present in the molecules of t... (Complete abstract click electronic access below) / Mestre