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.

Transfer of radionuclides from soil to vegetation in selected Irish ecosystems

This thesis details the findings of a study relating the transfer of 238U, 228Ra (232Th), 226Ra, and 137Cs from soil to vegetation in an Atlantic blanket bog, upland blanket bog and semi-natural grassland situated along the north-west coast of Ireland. The results of this study provide information on the uptake of these radionuclides by the indigenous vegetation found present in these ecosystems. The ecosystems chosen are internationally recognizable ecosystems and provide a wide variety of vegetation species and contrasting soil physiochemical properties which allow the influence of these parameters on radionuclide uptake to be assessed. The levels of radionuclides in the soil and vegetation were measured using gamma spectrometry, alpha spectrometry and ICP-MS. The nutrient status of the vegetation and soil physiochemical properties were measured using atomic absorption, flame photometry and other analytical techniques. The results of the study indicate that the uptake of 238U and 228Ra (232Th) by vegetation from all three ecosystems was negligible as the levels in all vegetation was below the limits of detection for the methods used in this study. These results appear to indicate that the vegetation studied do not possess the ability to accumulate significant levels of these radionuclides however this assumption cannot be upheld in the case of the Atlantic blanket bog as the levels in the soil of this ecosystem were too low for detection. Similar results were obtained for 226Ra uptake in both the Atlantic blanket bog and grassland for all vegetation with the exception of H. lanatus from the grassland ecosystem. Radium-226 uptake in upland blanket bog was higher and was detectable in the majority of vegetation indigenous to this ecosystem. Transfer factor values ranged from 0.07 to 2.35 and the TF values for E. tetralix were significantly higher than all other vegetation studied. This species of heather demonstrated the ability to accumulate 226Ra to a greater extent than all other vegetation. The uptake of 226Ra by upland blanket bog vegetation appears to be significantly influenced by a range of soil physiochemical properties. The nutrient status of the vegetation, in particular the calcium content in the vegetation appears to have a negative impact on the uptake of this radionuclide. Potassium-40 was detectable in all vegetation present in the three ecosystems and the levels in the grassland soil were significantly higher than the levels in both bogland soils. Transfer factor values for Atlantic blanket bog vegetation ranged from 0.9 to 13 .8 and were significantly higher in E. vaginatum in comparison to C. vulgaris. Potassium-40 TF values for upland blanket bog vegetation on average ranged from 1.4 for C. vulgaris (stems) to 5.2 for E. vaginatum and were statistically similar for all species of vegetation. Transfer factor values for grassland vegetation ranged from 0.7 to 3.8 and were also statistically similar for all species of vegetation indicating that the transfer of 40K to vegetation within the upland bog and grassland ecosystem is not dependent on plant species. Comparisons of 40K TF values for all three ecosystems indicate that the uptake in E. vaginatum from the Atlantic blanket bog was statistically higher than all other vegetation studied. This appears to indicate that E. vaginatum has the ability to accumulate 40K, however, this species of vegetation was also present in the upland blanket and did not demonstrate the same behaviour. The uptake of 40K by vegetation from all three ecosystems was significantly affected by a range of soil physiochemical properties and in some cases the results were contradictory in nature possibly indicating that the affect of these parameters on 40K uptake is species dependent. The most obvious trend in the data was the influence of soil CEC and magnesium levels in vegetation on 40K TF values. A positive correlation was apparent between the CEC of the soil and 40K uptake in vegetation from both the Atlantic blanket bog and grassland ecosystem. A similar trend was apparent between magnesium levels in vegetation and 40K TF values for the upland blanket bog and grassland vegetation. Caesium-13 7 levels were found to be significantly higher in the two bogland soils in comparison to the grassland soil and levels of 137Cs decreased with increasing soil depth. Transfer factor values for Atlantic blanket bog vegetation ranged from 1.9 to 9.6 and TF values were significantly higher in the leaves o f C. vulgaris in comparison to all other vegetation from this ecosystem. Caesium-13 7 TF values for the upland blanket bog vegetation on average ranged from 0.29 for E. tetralix to 1.6 for C. vulgaris. Uptake by the leaves of C. vulgaris was significantly higher than all other vegetation present thereby supporting the trend found within the Atlantic blanket bog vegetation. These results appear to indicate that the leaves of C. vulgaris have the ability to accumulate significant quantities of 137Cs and also that the uptake of 137Cs by this vegetation is dependent on plant compartment as the stems of this vegetation contained significantly lower levels than the leaves in both ecosystems. The uptake of 137Cs by grassland vegetation was very low and was only detectable in a fraction of the vegetation sampled. Caesium-137 TF values for grassland vegetation were in general lower than 0.02. The impact of soil physiochemical properties and nutrient status of vegetation on 137Cs uptake by vegetation appears to be complex and in some cases contradictory. The most apparent trend in the data was the positive influence of vegetation nutrients on 137Cs uptake in particular the magnesium levels present in the vegetation and to a lesser extent the calcium levels present. The results in general indicate that the uptake of 226Ra, 40K and 137Cs by the chosen vegetation is varied and complex and is significantly dependent on the species of vegetation, soil radionuclide concentration, soil physiochemical properties and the nutrient status of the vegetation.

Nutritional composition, quality and spoilage capacity of orange roughy (Hoplostethus atlanticus) from the North East Atlantic

The nutritional composition o f orange roughy (collected from the Northeast Atlantic near the Rockall Trough) was studied on a seasonal basis. In addition samples were aged and stability assessed. Protein levels (16.68-16.21% w/w) were found to be slightly higher than those recorded for the N ew Zealand species o f orange roughy and compared favourably with protein values for fish muscle in general. Statistically results show a significant seasonal variation with no variation from fish to fish or in the location within the fish. Lipid content (3.6-4.5% w/w) was found to be much lower than that recorded for New Zealand. As with protein statistically results show a significant seasonal variation and no variation from fish to fish or in the location within the fish. Moisture levels (77.3_79.6%w/w) compared favourably with values obtained from other studies. Again statistically results show a significant seasonal variation with no variation from fish to fish or within the fish. Iodine values (74.63-79.54) indicate the likely presence o f a high level o f mono unsaturated fatty acids. Statistically results show no significant seasonal variation and no sample variation or variation within fish. Thin layer chromatography o f the extracted fat showed the major type to be wax esters with a much lower amount o f triglycerides and smaller amounts of polar lipids, free sterols and free fatty acids. Total fatty acid composition was found to be very similar to that recorded from other studies and showed that most o f the oils extracted from the fish muscle contained a high percentage o f mono unsaturates namely 16:1,18:1, 20:1 and 22:1 (85.63 - 91.14% ) with 16:1 present in the smallest amounts and 18:1 the major one. The only saturated fatty M.Sc. in Biochemistry III Nutritional Composition, Quality and Spoilage Capacity of Specific Deep Sea Fish acids present in significant quantities were 14:0, 16:0 and 18:0, the total varied from a seasonal average high o f 4.05 % to an average low o f 2.27%. The polyunsaturated fatty acids linoleic and arachidonic acid were present in small quantities varying in total from 0.89% to 1.50%. Docosapentaenoic acid (D P A ) was found only in trace quantities in spring, autumn and winter samples and undetected in summer. Levels o f Eicosapentaenoic acid (EPA ) and Docosahexaenoic acid (D H A ) were also found in very low percentages and varied on a seasonal basis with average values ranging from 0.41% in summer to 1.03 % in autumn for EPA and from 1.44 % in summer to3.20 % in autumn for D H A . Again statistically results show a significant seasonal variation with no variation from fish to fish or location within the fish. Levels o f freshness were measured using the Thiobarbituric acid (T B A ), Total volatile base nitrogen (T V B -N ) and Trimethylamine (T M A ) techniques. The quality o f the fish upon arrival was excellent and well below legal/acceptable lim its.T V B -N values ranged from 6.88-8.91 mg/lOOg and T M A values from 4.82-6.46 mg/lOOg Values for T B A ranged from 0.18-0.35 mg Malonaldehyde/kg fish. The summer values were higher than the other seasons. Seasonal variation was significant for all methods with no variation from fish to fish or within the fish. Fish aged at +4°C in air did not exceed the T V B N lim it o f 35mg/100g until day 6 whereas the T V B N lim it was extended to 8 days for fish aged at +4°C in vacuum. However the T M A lim it o f 12mg/100g was reached on day 4 for fish stored at +4°C in air and on day 5 for vacuum packed samples stored at +4°C . Fish stored at -5°C in air and vacuum packed did not reach the T V B N lim it until day 61 but the T M A limit was reached on day 24 for fish stored at -5°C in air and was extended to 31 days for vacuum packed fish stored at-5°C. Prolonged storage at -18°C caused some deterioration o f the frozen fish muscle. Upon thawing the shelf life o f fish stored for 12 months was much shorter than that stored for 6 M.Sc. in Biochemistry IV Nutritional Composition, Quality and Spoilage Capacity of Specific Deep Sea Fish months. This in turn deteriorated faster than fresh fish held at refridgeration temperature in air. Orange roughy were found to be a good source of protein with moisture levels similar to that o f other fish. They were o f medium fat content but have a very poor content o f the essential omega 3 and omega 6 fatty acids. Orange roughy can be stored at -18°C but its subsequent refridgerated shelf life will be shorter than that o f unfrozen orange roughy stored at refridgeration temperature. Orange roughy are a very important part o f the ecosystem. Their composition is less nutritionally beneficial than more readily available fish for human consumption and therefore should not be fished at all