Abstract
This thesis has developed a suite of compound specific stable isotope tools to monitor landfill leachate and identify the infiltration of leachate to ground water and surface water. These tools have the power to indicate the fractional contribution multiple discrete sources of pollution are making to a single location. This journey began by developing two solid phase extraction (SPE) methods to extract non-polar and polar organic compounds from leachate with minimal fractionation of hydrogen or carbon isotopes. Non-polar compounds were successfully extracted using ENV+ SPE cartridges and polar compounds were successfully extracted using Strata-X SPE cartridges. The isotopic fractionation of non-polar compounds during ENV+ extraction varied significantly (up to 245⁰/₀₀ and 1.8⁰/₀₀ for D and ¹³C respectively, when eluted with acetonitrile and ethyl acetate, as recommended by manufacturers) but the fractionation of compounds eluted with dichloromethane was negligible (less than instrumental precision). Polar compounds were eluted from Strata-X cartridges with negligible isotopic fractionation using methanol. The direct comparison of SPE and liquid-liquid extraction found SPE to extract slightly more compound from leachate then liquid-liquid extraction (especially for polar compounds) and the isotopic compositions of compounds did not change with extraction methods.
These new analytical methods subsequently were used to determine the isotopic compositions of organic compounds dissolved in leachates from three New Zealand landfills. The molecular and isotopic signature of leachate varied significantly between landfills, indicating the isotopic fingerprint of organic compounds in leachate is unsuitable as a universal tracer of leachate. However, compounds such as terpien-4-ol, methylethylbenzene and juvabione maintained their isotopic composition over short geographical distance-indicating their potential as site-specific tracers of leachate. Organic compounds analysed on a transect across the landfill boundary indicated polar compounds were more mobile than semi-volatile compounds and possessed a more conservative isotopic composition. However, hexadecanoic acid extracted from leachate and ground water was highly depleted in ¹³C (-72 ⁰/₀₀ to -40⁰/₀₀), indicative of methanogenic and sulfate reducing bacteria. These bacteria only live in highly reducing environments such as leachate; therefore their presence in the pristine environment can potentially indicate the release of leachate from the landfill.
The final experiments traced the uptake and utilisation of leachate by periphyton. The isotopic composition of bulk periphyton, fatty acids and phytol indicated that microbial assimilation and utilisation of nutrients is a complex process. Fatty acid biomarkers for green algae and diatoms showed signs of leachate derived nutrients, however the availability of nutrients (carbon, nitrogen, water and light) caused significant changes in metabolic processes and isotopic compositions. Under slow growing conditions, the [delta]¹³C composition of periphyton became enriched in ¹³C as solar irradiation levels decreased (including shading by detritus and periphyton), while the [delta]D composition of fatty acid was controlled by the internal recycling of hydrogen. This study indicated the power of compound specific isotope analysis as a tool to detect the release of landfill leachate from a landfill, especially at locations with multiple potential sources of contaminants, and provides a sound platform for future research.