Thesis (M.Sc.)--College of William and Mary. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Drexel University, 2005. / Includes abstract and vita. Includes bibliographical references (leaves 191-199).

No description available.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 167-178). Available also in a digital version from Dissertation Abstracts.

Thesis (M.S.)--The University of North Carolina at Greensboro, 2010. / Directed by Anne Hershey; submitted to the Dept. of Biology.

Neodymium (Nd) isotopes have been increasingly used to trace the modern and past ocean circulation. This assumes that seawater Nd isotope ratios (εNd) effectively fingerprint different water masses and approximate expected values from water mass mixing. However, the decoupling of Nd isotopes and Nd concentration (the “Nd paradox”) in the water column, and the lack of understanding of sources and sinks of Nd, restrain our understanding of the “quasi-conservative” behavior of εNd in seawater. Nd is one of the lanthanide rare earth elements (REEs) with similar chemical characteristics that undergo some degree of fractionation. The shale-normalized REE patterns and REE ratios can be used to investigate potential sources/sinks of REEs. Combining REEs with εNd will provide additional information to study REE cycling in the ocean. To better understand the reliability of εNd as a water mass tracer, 17 high-resolution seawater profiles were sampled meridionally in the Southwest Atlantic (GEOTRACES GA02 Leg 3; RRS James Cook 057) and measured for εNd. This region involves the major water masses in the Atlantic Meridional Overturning Circulation: southward flowing North Atlantic Deep Water (NADW), northward flowing Antarctic Intermediate Water (AAIW) and Antarctic Bottom Water (AABW). Along the cruise track, there are potential sources (eolian dusts, marginal sediments, oceanic volcanism, and nepheloid layer) that could add external Nd to seawater and disturb the “quasi-conservative” behavior of εNd. Our results show strikingly that the Southwest Atlantic transect confirms “quasi-conservative” behavior of εNd in intermediate and deep water. Our evaluations of Nd isotopic deviations (ΔεNd) from conservative behavior show that out of 198 intermediate and deep samples, 49% of ΔεNd-values are within ± 0.25 εNd units (< analytical error: ± 0.30 εNd units) and 84% of ΔεNd-values are within ± 0.75 εNd units. Potential sources that could add external Nd to seawater from oceanic volcanism and the nepheloid layer do not show impact on seawater εNd. Terrigenous sources of Nd (e.g. eolian dusts from Africa and Patagonia, marginal sediments from South America) show influence on surface/subsurface water εNd but this εNd signature is not transferred to intermediate and deep water. To better understand the conservative vs. non-conservative behavior of REEs in the ocean, the dissolved REE concentrations were analyzed for the 17 seawater profiles in the Southwest Meridional Atlantic Transect (GEOTRACES GA02 Leg 3). The shale-normalized REE patterns are consistent with typical seawater patterns. To investigate whether and how much REE concentrations deviate from conservative water mass mixing, the REE concentration deviations were calculated for the intermediate and deep water. It is shown that within the SAMT, the intermediate and deep water REEs generally reflect water mass mixing and nearly conservative behavior. Along this transect, the potential sources that could add external REEs to seawater are dissolution of REEs from eolian dust to the surface/subsurface water, REEs released from dissolution of Fe-Mn oxides in the oxygen depleted zone, REEs from sediments near the continental margin, and dissolution of REEs from deep sea sediments. REEs and Nd isotopes of most intermediate and deep water masses passing the volcanic Rio Grande Rise (RGR) and Vitória-Trindade Ridge (VTR) do not show influence from RGR and VTR. REEs and Nd isotopes of the bottom water Lower Circumpolar Deep Water (LCDW) and AABW passing the RGR are influenced by dissolved REEs from the deep sea sediments. LCDW and AABW passing the VTR are influenced by dissolved REEs from the deep sea sediments as well as the volcanic VTR. In order to better understand the oceanic Nd cycling in the North Pacific, its sources and sinks in seawater must be better characterized. The high εNd of North Pacific Deep Water (NPDW, ~ −4) has been difficult to reconcile with the eolian inputs as reflected in surface waters (e.g. Jones et al., 2008), which have much lower εNd (~ −10), indicating potential addition of a component from Pacific volcanism. In order to constrain the REE sources in the North Pacific, we measured εNd and REEs of seawater from five stations across the subarctic North Pacific sampled by the Innovative North Pacific Experiment (INOPEX) Cruise SO202 (2009). In the surface water (~10 m), the highest εNd is observed at the station closest to the Aleutian-Kamchatka volcanic margin (Northwest station SO202-5), suggesting higher contribution of external REEs from volcanic ashes compared to the other stations. In the shallow water (100-400 m, depending on location), remineralization of REEs from volcanic ashes prevails over Asian dusts at Northwest station SO202-5 and near Japan stations SO202-44, 41, and 39, whereas remineralization of REEs from Asian dusts prevails over volcanic ashes at the Northeast station SO202-32 in the open ocean of the Alaska Peninsula. From the depths of North Pacific Intermediate Water (NPIW) to NPDW, seawater εNd and REEs show conservative water mass mixing of NPIW-NPDW. They also show conservative behavior along the water mass transport paths of NPIW and NPDW. Below the depths of NPDW, addition of external REEs is observed in the vertical profiles of εNd and REEs as well as along the transport path of LCDW. The potential sources that add external REEs to the bottom water are (1) sediments on the Kuril-Kamchatka-Aleutian volcanic margin along the LCDW transport path, and (2) sediments on the seafloor, both of which could interact with seawater and modify the seawater εNd and REE signatures.

The present study aimed to determine whether stable isotope techniques can be universally applied to detect landfill leachate contamination in aquatic systems. Results of analysis of ��C in dissolved inorganic carbon ([delta]��C-DIC), deuterium and �⁸O in water ([delta]D-H₂O and [delta]�⁸O-H₂O), and �⁵N of dissolved inorganic nitrogen components ([delta]�⁵N-NH₄⁺ and [delta]�⁵N-NO₃⁻) were presented for leachate, surface, and ground water samples collected from seven landfills located throughout New Zealand between 2003 and 2006. The unique conditions within a landfill lead to measurable fractionations in the isotopic ratios of the products of degradation. Results of isotope and ancillary parameter analyses enabled the discernment of different types of leachate, resulting from different microbial processes within the landfill environment. The isotopic characterisation of leachate enabled improved interpretation of geochemical data from potentially impacted surface and ground waters, and provides useful insight to landfill development for landfill operators. A general isotopic fingerprint delineated by [delta]��C-DIC and [delta]D-H₂O values showed leachate to be isotopically distinct from uncontaminated surface and ground water for samples analysed in the present study. However, not all water samples identified as leachate-impacted via site-specific assessments exhibited isotopic values that overlapped with the general leachate fingerprint. This highlights the need to investigate each site individually, within the context of a possibly global leachate isotope signature. Site-specific investigations revealed the effectiveness of applying [delta]�⁸O-H₂O and [delta]�⁵N-NH₄⁺ or [delta]�⁵N-NO₃⁻, in addition to [delta]��C-DIC and [delta]D-H₂O analyses, to the detection of leachate impact on aquatic systems. Furthermore, ancillary parameters such as alkalinity and ammonium concentration enabled the construction of simple isotope mixing models for an estimate of the quantity of leachate contribution. Results of isotopic investigations of stream biota suggested potential for the development of bio-indicators to monitor leachate influence on aquatic ecosystems in landfill-associated streams. The present study demonstrated the probative power of stable isotope techniques applied to investigations of leachate impact on landfill-associated aquatic systems.

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 ��C 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 ��C (-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]��C composition of periphyton became enriched in ��C 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.

The present study aimed to determine whether stable isotope techniques can be universally applied to detect landfill leachate contamination in aquatic systems. Results of analysis of ��C in dissolved inorganic carbon ([delta]��C-DIC), deuterium and �⁸O in water ([delta]D-H₂O and [delta]�⁸O-H₂O), and �⁵N of dissolved inorganic nitrogen components ([delta]�⁵N-NH₄⁺ and [delta]�⁵N-NO₃⁻) were presented for leachate, surface, and ground water samples collected from seven landfills located throughout New Zealand between 2003 and 2006. The unique conditions within a landfill lead to measurable fractionations in the isotopic ratios of the products of degradation. Results of isotope and ancillary parameter analyses enabled the discernment of different types of leachate, resulting from different microbial processes within the landfill environment. The isotopic characterisation of leachate enabled improved interpretation of geochemical data from potentially impacted surface and ground waters, and provides useful insight to landfill development for landfill operators. A general isotopic fingerprint delineated by [delta]��C-DIC and [delta]D-H₂O values showed leachate to be isotopically distinct from uncontaminated surface and ground water for samples analysed in the present study. However, not all water samples identified as leachate-impacted via site-specific assessments exhibited isotopic values that overlapped with the general leachate fingerprint. This highlights the need to investigate each site individually, within the context of a possibly global leachate isotope signature. Site-specific investigations revealed the effectiveness of applying [delta]�⁸O-H₂O and [delta]�⁵N-NH₄⁺ or [delta]�⁵N-NO₃⁻, in addition to [delta]��C-DIC and [delta]D-H₂O analyses, to the detection of leachate impact on aquatic systems. Furthermore, ancillary parameters such as alkalinity and ammonium concentration enabled the construction of simple isotope mixing models for an estimate of the quantity of leachate contribution. Results of isotopic investigations of stream biota suggested potential for the development of bio-indicators to monitor leachate influence on aquatic ecosystems in landfill-associated streams. The present study demonstrated the probative power of stable isotope techniques applied to investigations of leachate impact on landfill-associated aquatic systems.

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 ��C 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 ��C (-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]��C composition of periphyton became enriched in ��C 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.