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This thesis reports an investigation into methods of determining the long term deposition field for atmospheric aerosols in areas of complex topography using the soil inventories of atmospherically derived radionuclides. Measurements of the radionuclides ²¹⁰Pb, ¹³⁷Cs, ¹³⁴Cs and ⁷Be in vegetation and soil have been made at five mountain locations in northern Britain. A description of the field sampling procedure, sample processing and y-ray analysis is given. Loss-on-ignition experiments to determine the organic fraction of sampled soils were also conducted on selected samples. The presence of frequent low level cloud shrouding mountain tops in the uplands of northern and western Britain leads to enhanced precipitation and also deposition of the major acidic ions, eg SO₃²⁻ and N0₃, due to the washout of the low level cloud by falling rain ('seeder-feeder scavenging') and also the direct deposition of cloud droplets ('occult deposition'). It is important to quantify the inputs of acidic deposition in these acid sensitive regions and direct measurements present many logistical problems. The radionuclide ²¹⁰Pb is attached to the same sub-micron aerosol size range in the atmosphere as the major acidic ions and following deposition attaches very strongly to organic matter in soils. In this study the soil inventory of atmospherically derived ²¹⁰Pb is used as a tracer of the deposition of acidic ions. As the half-life of ²¹⁰Pb is 22.3 years the soil inventory of ²¹⁰Pb(atmos), at a site undisturbed for - 100 years, represents deposition integrated over several decades. Initial sampling took place at the Merrick, an isolated mountain close to the coast in southwest Scotland, to test and develop the technique. Measurements showed the ²¹⁰Pb(atmos) inventory to increase with altitude at a greater rate than precipitation. Sampling at Great Dun Fell in Cumbria enabled the measured radionuclide inventories to be compared with detailed measurements of the variation of the wet deposition pattern with altitude, and also with a model of sulphate deposition. Close correspondence was found between the ²¹⁰Pb deposition profile and the deposition pattern, with altitude, for the major acidic ions. The three mountains Ben Cruachan, Beinn Dorain and Ben Lawers lie along an 80 km transect running roughly west to east from the western coast into the central Highlands. Sampling at these three mountains has yielded information on the change in the wet deposition field with distance inland. The measurements suggest that deposition of ²¹⁰Pb decreases, with distance from the western coast, at a greater rate than does precipitation. The soil inventory of ²¹⁰Pb(atmos) increases with altitude at a greater rate than rainfall at 4 of the 5 mountains. The results show that, around summits, on average, the concentration of ²¹⁰Pb in low level cloud is a factor of - 2 greater than in the frontal ('seeder') rain falling from higher altitude. This finding is in good agreement with detailed wet deposition measurements. The ²¹⁰Pb measurements are important in themselves as they help define the global and UK ²¹⁰Pb budget. From measurements made at 65 individual sites the mean ²¹⁰Pb(atmos) inventory is 0.44 ± 0.03 Bq cm⁻², with the mean of the average annual rainfall being 2,060 ± 70 mm yr⁻¹. These figures correspond to a mean concentration of ²¹⁰Pb in rainfall of 66 mBql⁻¹. The ¹³⁷Cs inventory has been separated into the fraction originating from nuclear weapons testing, ¹³⁷Cs(bomb), and the fraction due to the Chernobyl accident, ¹³⁷Cs(Chern). The measured ¹³⁷Cs(bomb) inventory ranges from a mean of 3,300 Bq m⁻² at Ben Lawers to 5,200 Bq m⁻² at Beinn Dorain. The ¹³⁷Cs(Chern) inventory is highly variable between locations ranging from a mean of 440 Bq m⁻² at Great Dun Fell to 14,900 Bqm⁻² at Ben Lawers reflecting the patchy nature of deposition, due largely to convective storms, during the passage of the radioactive plume. The radionuclide ¹³⁷Cs is shown to be relatively mobile in the organic soils which characterise the study areas. The cosmogenic radionuclide ⁷Be was measured in samples collected from the Merrick on 26th Oct 1988. The mean inventory was 0.039 Bq cm⁻², being associated with vegetation and the top few cm of the soil profile.

Understanding the transport and retention of radionuclides in the environment is important for protecting freshwater supplies and minimizing impact to biologic systems. Technetium-99 (Tc⁹⁹) is a radionuclide of interest due to its long half-life (2.13 x 10⁵ years) and toxicity. In the form of pertechnetate (TcO₄⁻), Tc is expected to move nearly unretarded in the subsurface. Under reducing conditions Tc can precipitate in low solubility Tc oxide (TcO₂·nH₂O) and/or Tc sulfide (Tc₂S[subscript x]) phases. The studies presented in this dissertation investigate the physiochemical mechanisms for the transport and retention of Tc. Transport studies determined that TcO₄⁻ would move at pore water velocity in unsaturated sediments. Geochemical studies of contaminated sediments determined that nearly ~ 25 % of the total Tc was retained in phases associated with iron oxide and aluminosilicate minerals, thus reducing the mobility of Tc. Studies of Tc₂S[subscript x] mineral phases, generated using nano Zero Valent Iron (nZVI) and sulfide (HS-) in sediments, determined that Tc could be stabilized in mineral phases as Tc₂S[subscript x] that were slower to reoxidize than TcO₂·nH₂O phases. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Feb. 14, 2013 - Feb. 14, 2014