Thesis advisor: Amy Frappier / Tropical cyclones (TCs), known as hurricanes in the Atlantic and Typhoons in the Pacific, are among the most destructive and deadly natural disasters that occur on Earth. Attempts to understand how TCs relate to the global climate system, and future risk assessments are dependent upon having records of TC activity that pre-date the modern meteorological records, which are commonly not older than 130 years (Nott, 2003). Paleotempestology is a sub-discipline of paleoclimatology that attempts to extend the TC record beyond the meteorological record through the use of proxies. Presented here is the establishment of a paleotempestology proxy based on clastic mud being suspended in the water column by floods caused by TCs and deposited in stalagmite CH-1, collected in June of 2007 from Cenote Chaltun-Ha, a low-lying cave from the Yucatán Peninsula. CH-1 was dated by a combination of <super>210</super>Pb, U/Th, and layer counting techniques, creating an age model for its entire length. The years with mud layers were compared to the historical TC record from 1852-2006. Nineteen mud layers were identified for this time period. All of the mud layers deposited in years with at least one TC passing within 330 km of Cenote Chaltun-Ha. A total of 265 mud layers were identified in CH-1 dating from 198 BC to 2006 AD. Relatively high TC frequency, ~16 mud layers/century, was recorded in CH-1 from 198 BC to ~1233 AD. This period was followed by eight centuries of relatively low TC frequency, ~7 mud layers/century. The low frequency period hit a low point in the 1600s with 4 mud layers. Since the 1600s the TC frequency recorded in CH-1 has been on the rise, indicating possible periods of higher than present TC frequency in the future for the Yucatán region. This trend of high TC frequency followed by a sudden drop and subsequent increase is also reported in published sand overwash deposit research. &#948;;<super>18</super>O and &#948;;<super>13</super> values collected from CH-1 provide insight into the timing of regional droughts. A low &#948;;<super>18</super>O value from 1815 provides evidence that "The Year Without a Summer" caused by the 1815 eruption of the Tambora volcano in Indonesia had a climatic effect on the Yucatán. A land-use signal related to the agricultural production boom of Agave Fourcroydes, a succulent plant known as Henequen, in the early 20th century was also detected in &#948;;<super>13</super>C values. / Thesis (MS) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Geology and Geophysics.

This study applies a life history approach to analyzing the identities of 52 Maya individuals who lived between 2000 BC and AD 900 in and around the city of Holmul, within the Petén region of Guatemala. Primary goals were to: (1) identify migrant and local individuals within the urban population; (2) determine 87Sr/86Sr isotope ratio signatures for the sites of Holmul, Cival, La Sufricaya, K’o, and Hamontun; (3) compile osteobiographies, personal life histories revealed through skeletal remains, of the individuals in the sample; and (4) evaluate evidence bearing on the identities of inhabitants of the Holmul region and how they were represented within economic, political, and cultural landscapes of the ancient Maya. This work demonstrates how bioarchaeologists can implement osteobiographical analyses to advance the understanding of multifaceted social identities and individual experiences of life and death. By integrating osteological study, stable isotope analysis, and consideration of mortuary context, material culture, inscriptions, and monumental architecture, the individual, rather than the population, becomes the focus. This aggregate approach allows for an in-depth consideration of human remains as former social beings with complex identities. The findings of this research suggest that most elite inhabitants in this ancient Maya city were local to the Holmul region, with the few outliers having originated from elsewhere in the Maya lowlands. This conclusion aligns with Maya elite ideologies of establishing lineages and reinforcing power through ancestor veneration. The local 87Sr/86Sr ratio signature of the Holmul region is comparable to other archaeological sites in the southern Maya lowlands. The osteobiographies reveal life histories, which personalize prior interpretations that considered the population only as an aggregate. This project also elucidates identities of sacrificed children, elite/royal women, and the local Holmul elite. Results of the study support the use of the isotopic analysis of human remains as an essential tool for approaching complex archaeological questions and evaluating hypotheses previously addressed primarily using architectural, iconographic, and artifactual evidence. Further, this study demonstrates the benefit of the isotopic analysis of dental enamel, especially in the Maya region and other environments characterized by difficult excavation conditions and the poor preservation of human remains.

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.

Food webs in aquatic ecosystems can be dramatically altered by invasive species. Quagga mussels are prevalent invaders that compete with existing species and disrupt nutrient cycling. In 2012, the Quagga Mussel (Dreissena rostriformus bugensis) was introduced into Lake Powell and is expected to move throughout the reservoir in the near future. Stable isotope analysis is a powerful tool for characterizing food webs and trophic interactions. To predict the long-term effects of Quagga Mussels, we used stable isotope analysis of primary producers, primary consumers, prey fish species, and predator fish species in Lake Powell to determine food web structure. Quagga Mussel are positioned to disrupt the pelagic arm of the food web by interfering with the link between phytoplankton and herbivorous zooplankton. This will likely have negative impacts on pelagic fish such as striped bass (Morone saxatilis) and threadfin shad (Dorosoma petenense). Quagga Mussel may also boost benthic productivity in the littoral zone by diverting nutrients from the water column to the benthos. This may have positive impacts on littoral fishes such as largemouth bass (Micropterus salmoides), smallmouth bass (Micropterus dolomieu), bluegill (Lepomis macrochirus), and green sunfish (Lepomis cyanellus).

Sea surface temperature (SST) reconstructions from the low latitudes indicate the tropics/subtropics warmed significantly before glacial-interglacial decreases in global ice volume, suggesting the importance of tropical and subtropical climate in driving glacial terminations. ODP Site 625, drilled at a water depth of 889 m near De Soto Canyon in the Gulf of Mexico (GOM), provides continuous records of marine isotope stages (MIS) 1-6 sampled at a mean temporal resolution of 400 years. Age control is based on 8 AMS radiocarbon dates, marine isotope stratigraphy, and Foraminifera datum levels. Results from Globigerinoides ruber (white variety) Mg/Ca-SST indicate a rise of 4.4 °C from last glacial maximum to modern conditions and a 3.2 °C rise from the penultimate glaciation to the last interglaciation. However, model results suggest reduced thermohaline circulation (THC) causes salt and heat build-up in the Atlantic Warm Pool. Paired G. ruber Mg/Ca-SST and δ18O provide evidence of sub-millennial scale variability in GOM SST and SSS that is probably influenced by the strength of NADW production, as also observed in the Western Caribbean Sea. We test the idea that widespread abrupt climate change during the last glaciation caused by millennial scale fluctuations in the intensity of THC was modulated by Laurentide ice sheet (LIS) meltwater routed to the North Atlantic. To understand LIS melting dynamics and test the Meltwater Routing Hypothesis, we investigate the phasing of GOM SST and LIS freshwater events in relationship to high latitude climate. Estimated salinities from our multi-proxy approach suggest three freshwater events with a major freshwater influx from that occurred during Heinrich Event 2. This result confirms previous studies that suggested LIS summer melting during warmings in Antarctica. We also find a climate reversal during termination II from 130.4-128.4 ka. The initial rise in GOM SST at 132.1 ka of 2.9 °C is followed by a cold reversal of 1.5 °C at 130.4 ka for 2 ky and final increase to full interglacial warmth. The reversal in GOM SST is consonant with a pause in sea level rise and reduced NADW, suggesting a reduction in THC may have caused a global two-step deglaciation.

Blooms of the red tide dinoflagellate Karenia brevis occur annually on the west Florida shelf. In the late summer/early fall months, background concentrations increase from 103 cells L-1 to excesses of 106 cells L-1. Blooms are most common between Tampa Bay and Charlotte Harbor, and may be maintained for months. The region’s hydrography may play a role in the initiation, maintenance and termination of blooms. The west Florida shelf is depauperate in inorganic nutrients. Inorganic nitrogen and phosphorus rarely exceed the limits of detection, whereas dissolved organic nitrogen is often present at concentrations of 15 to 20 µM. Because K. brevis exhibits the ability to utilize both organic nitrogen and phosphorus, the organic pool may serve as an important nutrient source. The source of nutrients for K. brevis blooms is the focus of much scientific research. Nitrogen is considered to be the limiting nutrient in marine waters and may have several sources. Potential sources of inorganic and organic nitrogen are estuarine outflow, atmospheric deposition, upwelling, dissolved organic nitrogen released from N2 fixing cyanobacteria, diatom blooms, decaying seagrasses, fish or other organic matter. The natural abundance stable isotopic signatures of particulate bloom material (δ15N and δ13C) associated with K. brevis blooms during 1998 to 2001 was analyzed and compared with known isotopic values of potential nutrient sources. Data was analyzed from blooms occurring from 1998 to 2001. Extensive analysis of the 2001 bloom showed that the δ15N of bloom material ranged from 2 0/00 to 5 0/00. δ13C of bloom material ranged from -22 0/00 and -17 0/00. Non-bloom material was considerably more variable in both δ15N and δ13C. δ13C values were higher near shore than offshore during the 2001 bloom, suggesting lower dissolved inorganic carbon levels due to high temperature and/or high biomass. δ15N of bloom material fell within the range of the δ15N values of potential nitrogen sources. It appears that K. brevis utilizes the available nitrogen sources opportunistically, and that isotopically more depleted sources are more important. More enriched sources such as upwelled nitrate or sewage nitrogen can be excluded as significant sources based on the isotopic data.

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.

Four separate but complimentary studies investigated the role of grain sorghum as a predator source for Southern Rolling Plains cotton in 2001 and 2002. Objectives were to: (1) determine the timing and magnitude of predator movement between crops, (2) test putative causes of movement by manipulating prey levels at different stages of crop phenology, (3) explore the feeding and reproductive behavior of a common predator colonizing cotton, and (4) examine the effects of grain sorghum and uncultivated areas on cotton predator abundance at an area-wide scale. Rubidium mark-recapture experiments indicated grain sorghum fields produced a net predator gain for adjacent cotton. Analysis suggested two coccinellids, Hippodamia convergens Guérin-Méneville and Scymnus loewii Mulsant, were responsible for the overall pattern of predator movement. Predator movement into cotton did not appear to be concentrated at specific stages of sorghum phenology. Manipulations of aphid levels in field cages were used to determine if prey abundance or phenology influenced the movement of H. convergens into cotton. In both years, more lady beetle adults were collected on cotton during the latest stages of sorghum phenology. In the second year, relatively low aphid densities (15 per plant) appeared to influence the movement of beetles onto caged cotton. Carbon isotope ratios of H. convergens were used to assess adult feeding behavior after colonizing cotton and to determine if prey consumed in sorghum contributed to egg production in cotton. Though aphids were absent 2001, H. convergens adults stayed in cotton, did not produce eggs and apparently consumed few prey. Cotton aphids were present in 2002 and H. convergens isotope ratios changed from prey consumed in cotton. The isotope ratios of egg masses collected in 2002 indicated prey consumed in grain sorghum contributed very little to egg production in cotton. An area-wide pattern analysis suggested the abundance of grain sorghum and uncultivated areas both positively influenced cotton predator levels. While these landscape effects were less important overall than prey levels and cotton planting dates, in some sampling periods landscape composition appeared to be the most important factor in determining cotton predator levels.

This study conducts a multi-isotopic bioarchaeological analysis of the Avondale Burial Place (McArthur Cemetery), a recently discovered Emancipation-era African American cemetery near Macon, GA. Stable isotopic analyses were performed on available dental remains in order to reconstruct the diet and demography of the individuals buried at McArthur Cemetery. Specifically, δ18O and δ13C were characterized in tooth enamel and examined in tandem with collaborative osteological and mortuary analyses to reconstruct early-life diet and residential origin. The results suggest that members of the Avondale community buried in McArthur did not experience significant mobility, but rather resided in the area for most of their lives. Overall, these results greatly contribute to the genealogical research of McArthur Cemetery’s descendants as well as the fragmented history of the South by exploring whether the individuals in this community took part in the Great Migration following the Civil War.