The spatial analysis and speciation of uranium and thorium series radionuclides in the soil of the Cronamuck Valley, County Donegal, Ireland

This thesis details the findings of a study into the spatial distribution and speciation of 238U, 226Ra and 228Ra in the soils of the Cronamuck valley, County Donegal . The region lies on the north-eastern edge of the Barnesmore granite and has been the subject of uranium prospecting efforts in the past. The results of the project provide information on the practicability of geostatistical techniques as a means of estimating the spatial distribution of natural radionuclides and provide insight into the behaviour of these nuclides and their modes of occurrence and enrichment in an upland bog environment. The results of the geostatistical survey conducted on the area indicate that the primary control over the levels of the studied nuclides in the soil of the valley is the underlying geology. Isopleth maps of nuclide levels in the valley indicate a predominance of elevated nuclide levels in the samples drawn from the granite region, statistical analysis of the data indicating that levels of the nuclides in samples drawn from the granite are greater than levels drawn from the non-granite region by up to a factor of 4.6 for 238U and 4.9 for 226Ra. Redistribution of the nuclides occurs via drainage systems within the valley, this process being responsible for transport of nuclides away from the granite region resulting in enrichment of nuclides in soils not underlain by the granite. Distribution of the nuclides within the valley is erratic, the effect of drainage f lows on the nuclides resulting in localized enriched areas within the valley. Speciation of the nuclides within one of the enriched areas encountered in the study indicates that enrichment is as a result of saturation of the soil with drainage water containing trace amounts of radionuclides. 238U is primarily held within the labile fractions (exchangeable cat ions + easily oxidisable organics + amorphous iron oxides ) of the soil , 226Ra being associated with the non- labile fractions, most probably the resistant organic material. 228Ra displays a significant occurrence in both the labile and non- labile fractions. The ability of the soil to retain uranium appears to be affected largely by the redox status of the soil, samples drawn from oxidizing environments tending to have little or no uranium in the easily oxidisable and amorphous iron oxide fractions. This loss of uranium from oxidised soil samples is responsible for the elevated 226Ra /238U disequilibrium encountered in the enriched areas of the valley. Analysis of the data indicates that samples displaying elevated 226Ra/238U ratios also exhibit elevated 228Ra/238U ratios indicating a loss of uranium from the samples as opposed to an enrichment of 226Ra.

Investigation into the potential for establishing a self-sustainable wetland ecosystem over pyritic mine tailings

Research was conducted to investigate the potential for ecologically engineering a sustainable wetland ecosystem over pyritic mine tailings to prevent the generation of acid mine drainage. Ecological engineering is technology with the primary goal being the creation of self-sustainable ecological systems. Work involved the design and construction of a pilot-scale wetland system comprising three wetland cells, each covering 100 m2. Approximately forty tonnes of pyritic mine tailings were deposited on the base of the first cell above a synthetic liner, covered with peat, flooded and planted with emergent wetland macrophytes Typha latifolia, Phragmites australis, and Juncus effusus. The second cell was constructed as a conventional free water surface wetland, planted identically, and used as a reference wetland/experimental control. Wetland monitoring to determine long-term sustainability focused on indicators of ecosystem health including ecological, hydrological, physico-chemical, geochemical, and biotic metrics. An integrated assessment was conducted that involved field ecology in addition to ecological risk assessment. The objective of the field ecology study was to use vegetative parameters as ecological indicators for documenting wetlands success or degradation. The goal of the risk assessment was to determine if heavy-metal contamination of the wetland sediments occurred through metal mobilisation from the underlying tailings, and to evaluate if subsequent water column chemistry and biotic metal concentrations were significantly correlated with adverse wetland ecosystem impacts. Data were used to assess heavy metal bioavailability within the system as a function of metal speciation in the wetland sediments. Results indicate hydrology is the most important variable in the design and establishment of the tailings wetland and suggest a wetland cover is an ecologically viable alternative for pyritic tailings which are feasible to flood. Ecological data indicate that in terms of species richness and diversity, the tailings-wetland was exhibiting the ecological characteristics of natural wetlands within two years. Ata indicate that pH and conductivity in the tailings-wetland were not adversely impacted by the acid-generating potential or sulphate concentration of the tailings substrate and its porewater. Similarly, no enhanced seasonal impacts from sulphate or metals in the water column, nor adverse impacts on the final water quality of the outflows, were detected. Mean total metal concentrations in the sediments of the tailings-wetland indicate no significant adverse mobilisation of metals into the peat substrate from the tailings. Correlation analyses indicate a general increase in sediment metal concentration in this wetland with increasing water depth and pH, and a corresponding decrease in the metal concentrations of the water column. Sediment extractions also showed enrichment of Cd, Fe, Pb and Zn in the oxidisable fraction (including sulphides and organic matter) of the tailings-wetland sediments. These data suggest that adsorption and coprecipitation of metals is occurring from the water column of the tailings wetland with organic material at increasing depths under reducing conditions. The long-term control of metal bioavailability in the tailings wetland will likely be related to the presence and continual build-up of organic carbon binding sites in the developing wetland above the tailings. Metal speciation including free-metal ion concentration and the impact of physico-chemical parameters particularly pH and organic matter, were investigated to assess ecotoxicological risk. Results indicate that potentially bioavailable metals (the sum of the exchangeable and reducible fractions) within the tailings wetland are similar to values cited for natural wetlands. Estimated free-metal ion concentrations calculated from geochemical regression models indicate lower free-metal ion concentrations of Cd in the tailings wetland than natural wetlands and slightly higher free-metal ion concentrations of Pb and Zn. Increased concentrations of metals in roots, rhizomes and stems of emergent macrophytes did not occur in the tailings wetland. Even though a substantial number of Typha latifolia plants were found rooting directly into tailings, elevated metals were not found in these plant tissues. Phragmites also did not exhibit elevated metal concentrations in any plant tissues. Typha and Phragmites populations appear to be exhibiting metal-tolerant behaviour. The chemistry of the water column and sediments in Silvermines wetland were also investigated and were much more indicative of a wetland system impacted by heavy metal contamination than the tailings-wetland. Mean Dc, Fe, Mn, Pb and Zn concentrations in the water column and sediments of Silvermines wetlands were substantially higher than in the pilot wetlands and closely approximate concentrations in these matrices contaminated with metals from mining. In addition, mean sulphate concentration in Silvermines wetland was substantially higher and is closer to sulphate concentrations in waters associated with mining. Potentially bioavailable metals were substantially elevated in Silvermines wetland in comparison to the pilot wetlands and higher than those calculated for natural rive sediments. However, Fe oxy-hydroxide concentrations in Silvermines sediments are also much higher than in the pilot wetlands and this significantly impacts the concentration of free-metal ions in the sediment porewater. The free-metal ion concentrations for Pb and Zn indicate that Silvermines wetland is retaining metals and acting as a treatment wetland for drainage emanating from Silvermines tailings dam.