The Chukchi and Beaufort Sea shelves host diverse and productive seafloor ecosystems important for carbon and nitrogen cycling for the Arctic Ocean. The benthic food web transfers energy from primary producers to high trophic level organisms (e.g., birds, fish, and mammals), which are important for cultural practices and subsistence hunting by Native Alaskans. This work focuses on the trophic ecology of arctic food webs through use of several different approaches. First, variation in the natural abundance of stable carbon and nitrogen isotopes facilitated the identification of trophic pathways and, subsequently, allowed the comparison of trophic guilds and food webs from the Chukchi and Beaufort Seas. Compared to water column and sedimentary organic matter end-members, second trophic level grazers and suspension feeders were conspicuously ¹³C-enriched throughout the Chukchi Sea, which supports the hypothesis that microbial degradation of organic matter occurred prior to metazoan assimilation. Second, food web recovery from disturbances caused by exploratory oil drilling at the seafloor that had occurred approximately 20 years prior were assessed in both the Chukchi and Beaufort Seas. Based on isotopic trophic niche overlap between organisms common to drilled and reference sites in the Chukchi and Beaufort Seas, the oil drilling sites had similar food web structure, indicating recovery from the activity associated with the drilling process. Third, photosynthetic pigment biomarkers were used to better understand the diagenetic process, specifically focusing on how both microbial and metazoan grazing pathways degrade organic matter in relation to seasonal sea ice retreat in the Chukchi Sea. The benthic macrofaunal and microbial food web caused rapid degradation of organic matter upon the initial pulse of microalgal food sources to the seafloor. These diagenetic pathways are linked to the ¹³C-enrichment of residual organic matter, which corresponds to the stable isotope values measured in the benthic macrofauna. Lastly, high-precision liquid chromatography and spectrophotometry were compared for estimating sedimentary pigments in the marine environment. Substantial differences in pheopigment (chlorophyll degradation products) concentrations were observed between the two techniques, suggesting the need for revisions to the monochromatic spectrophotometric equation that relates absorbance to pigment concentrations. One pheopigment, pheophorbide, was found to interfere with the accuracy of the spectrophotometric equation and caused the overestimation of pheopigments. / text

Shell organic matrix proteins in fossils are valuable geochemical archives for studying ancient environments and food webs. Compound-specific studies of stable carbon isotope ratios offer particularly good resolution of trophic level of consumers and the identities of primary producers and can be used to detect diagenetic alteration of isotopic ratios. To interpret compound specific isotope data, however, controlled diet studies in the laboratory are needed to reveal trophic enrichment patterns of 13C in tissues and shell organic matter. This study examines the relationship between d 13C of 11 amino acids in diet, soft tissues, and shell organic matter in laboratory-cultured Strombus alatus, an herbivorous marine gastropod. The d 13C values of amino acids in this animal's foot and mantle tissues are consistently enriched in 13C relative to the diet. Phenylalanine (+1.8 ppm) and alanine (+3.8 ppm) showed the least fractionation between diet and tissues, while aspartic acid (+10.7 ppm) and glutamic acid (+14.6 ppm) showed the greatest enrichment. On average, nonessential amino acids exhibited greater enrichment than did essential amino acids (+7.1 ppm vs. + 4.1 ppm). Shell organic matter amino acids showed a very similar pattern, with aspartic and glutamic acids again showing the greatest enrichment (+7.2 ppm and +11.1 ppm respectively). Nonessential amino acids in shell (+4.9 ppm) were also more enriched than the essential amino acids (+3.5 ppm). Overall, the carbon isotopic compositions of amino acids in shell organic matrix appear to parallel those in animal tissue, validating the utility of employing this material as a surrogate for animal tissue in fossil samples. Interpreting trophic position information in consumers is difficult, however, as the variation in the magnitude of trophic enrichments for glutamic and aspartic acids between species, tissue types and diet is still poorly understood. As phenylalanine has the most consistent diet-consumer enrichments, the most suitable application for d 13C isotope analysis at this time is the reconstruction of base food sources.

In the first phase of this project, four decades of monthly resolved geochemical variations from two massive heads of Montastraea were used to explore the reproducibility of the geochemical signal in these two corals from Looe Key, Florida. The coral d18O and d13C records of the two corals have statistically indistinguishable mean values, which is not the case for the coral Sr/Ca records implying that nonenvironmental factors are influencing coral Sr/Ca. Calibration equations relating coral geochemistry variations to environmental variations at Looe Key are different from previously published equations for Montastraea. These calibration differences are not related to growth-related kinetic effects, but may reflect variations in seawater chemistry in the coastal waters of the Florida Keys. Additional studies are needed to identify the causes of the observed geochemical variability. In the second phase of this study, fourteen decades of monthly resolved geochemical variations in another Montastraea coral from Looe Key, Florida were compared to records of sea-surface temperature (SST). Coral Sr/Ca and d18O variations have a weak relationship with variations in SST and skeletal extension rates; however, many events in the Sr/Ca and d18O records are coincident with anomalies in SST, growth, or precipitation. Strong coupling exists between Sr/Ca and d18O in both anomaly and mean annual perspectives, which reflects the combined influence of SST and growth related processes on the geochemical signal. Separating these impacts proved to be problematic due to modest agreements with each forcing variable. In the final phase of this study, geochemical records from three, mid-Holocene(~5 ka) fossil Montastraea corals from the Dry Tortugas, Florida were compared with geochemical records from modern Montastraea corals from the same region to investigate temporal changes in climate. Stable isotopic records show significant changes through time, which can be interpreted in terms of environmental variation; however, large inter-coral variability between modern specimens of Montastraea precludes meaningful assessment of Sr/Ca. The pattern and mean d18O values in the fossil corals reflects changes in both temperature and salinity are reminiscent of centennial-scale variability present in other records from this region.

The primary focus of this thesis is to examine the relationship between diet, as reconstructed via stable isotope analysis, and bone lead levels, quantified by trace element analysis for individuals interred at the Royal Naval Hospital Cemetery (RNHC), A.D. 1793-1822, in Antigua, West Indies. Individuals of both African and European ancestries were recovered from this colonial-era cemetery, and samples from their remains were analyzed to determine stable carbon and nitrogen isotope values (as a proxy for diet), and bone lead levels. The data were then compared in order to elucidate any association among the variables. This investigation revealed that the relationship between diet and lead may have been affected by many variables including ancestry, status, agency, and duration of stay in the West Indies. However, from the results presented in this thesis, the strongest correlation between stable isotope signatures and bone lead levels is in the relationship between δ13Ccollagen and lead for individuals consuming a diet primarily consisting of C3 staple starches and C3 fed animals. A secondary focus of this thesis is to estimate the extent to which the individuals interred at the RNHC may have suffered from symptoms of lead poisoning. Through conversion of bone lead levels to blood lead levels, potential symptomatology may be estimated in order to determine the percentage of individuals from the population that may have experienced mild to severe lead poisoning. In this population, a majority of individuals had high enough blood lead levels that they may have suffered from a range of symptoms associated with exposure to lead, which is not inconsistent with historical assertions that lead poisoning was of considerable detriment to the health and well-being of individuals serving in the British military in the colonial Caribbean. This study provides further insight into the health and lifeways of lower-ranking naval personnel and enslaved labourers owned by the Navy in the late eighteenth and early nineteenth century West Indies.

A lack of well-distributed, high-resolution records of Late Quaternary Asian palaeomonsoon variability remains an outstanding issue for palaeoclimatologists, and is especially marked in remote regions such as the mountains of southwestern China (Wang et al., 2005). Characterising the nature, timing and magnitude of climate variability in southwestern China is essential for understanding the regional climate as a whole, and the potential social, economic and environmental impacts that may result from Asian monsoon system changes. The NERC-funded research presented in this thesis focuses on a high altitude lake sediment record obtained from Lake Shudu, Yunnan Province, China. The lake is located on the southeastern edge of the Tibetan Plateau. The primary aims of this research were to identify and examine key environmental and climatic shifts which occurred in southwestern China during the Late Pleistocene (Dali) - Early Holocene Period; to examine the possible drivers of these changes; and to compare the findings with other regional proxy records in order to better understand climate dynamics in southwestern China. These aims were chosen in order to test the hypothesis that Late Quaternary millennial to centennial scale climatic and environmental changes in southwestern China were driven by changes in solar insolation and / or glacial climate boundary conditions, characterised by stepwise increases in palaeomonsoon intensity. AMS 14C radiocarbon dates obtained from bulk sediment samples and pollen concentrations indicated that the seven metre core (06SD) that forms the focus of this research spans the last c. 22.6 ka cal. yr BP, making it one of the longest high-resolution Late Quaternary records available for southwestern China. 06SD was examined using a multi-proxy approach incorporating physical, organic and palaeoecological analyses. The record captures the shift from colder, drier Pleistocene (Dali) conditions to warmer, wetter Holocene conditions and is punctuated by two events. The first event, centred at c. 17.3 ka cal. yr BP, possibly represents a phase of warmer and / or wetter conditions in response to rising solar insolation during the deglacial period. The second event, commencing at c. 11.7 ka cal. yr BP, possibly denotes the Pleistocene - Holocene Boundary. Overall, the findings of this research support the view that during the Late Pleistocene, Asian summer monsoon strengthening was non-linear and driven by changes in glacial dynamics and / or solar insolation.

Blooms of nitrogen fixing cyanobacteria (NFC) occur in many freshwater and marine systems, including the Baltic Sea. By fixing dissolved nitrogen, they circumvent general summer nitrogen limitation, while also generating a supply of novel bioavailable nitrogen for non-diazotrophic primary producers and ultimately supporting secondary production. Elucidating trophic links between primary consumers and NFC is essential for understanding role of these blooms for secondary production. However, until recently, there was no reliable method to quantify individual prey species for zooplankter feeding in situ. The development of PCR-based methods to detect prey-specific DNA in the diet of consumers, including microscopic animals, allows identification and quantification of trophic linkages in the field. Using molecular diet analysis in combination with egg production measurements, biochemical markers of growth and condition; and stable isotope approach, we explored a possibility to determine (1) whether cyanobacteria are grazed and assimilated by mesozooplankters (Papers I and II), (2) which species/groups are particularly efficient consumers of cyanobacteria (Papers II and III), and (3) how feeding on cyanobacteria affects zooplankton growth and development (Paper I and III). Taken together, these laboratory and field observations, provided evidence that NFC contribute to feeding and reproduction of zooplankton during summer and create a favorable growth environment for the copepod nauplii (Paper I). The favorable growth conditions for juvenile copepods observed during NFC blooms were hypothesized to be mediated by picoplankton that take up bioavailable nitrogen exuded from cyanobacterial cells. This hypothesis found support in Paper II that provided quantitative estimates for the direct picocyanobacteria → mesozooplankton pathway, with highest weight-specific consumption observed in nauplii. Further, using field observations on zooplankton and phytoplankton development during a growth season in the northern Baltic proper, we found that NFC nitrogen is assimilated and transferred to zooplankton via both direct grazing and indirectly through grazing on small-sized phyto- and bacterioplankton (Paper III). Finally, these and other findings emphasizing the importance of NFC for Baltic Sea secondary production during growth season were synthesized to show that diazotrophic nitrogen enters food webs already at bloom initiation (Paper III) and is transferred via multiple pathways to pelagic and benthic food webs and, ultimately, to fish (Paper IV). / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Accepted.</p>

This thesis contributes increased knowledge about climate variability during the late Quaternary in the eastern Mediterranean. Results from a paleoclimate review reveal that regional wetter conditions from 6000 to 5400 years BP were replaced by a less wet period from 5400 to 4600 years BP and to fully arid conditions around 4600 years BP. The data available, however, show that there is not enough evidence to support the notion of a widespread climate event with rapidly drying conditions in the region around 4200 years ago. The review further highlights the lack of paleoclimate data from the archaeologically rich Peloponnese Peninsula. This gap is addressed in this thesis by the provision of new paleoclimate records from the Peloponnese. One stalagmite from Kapsia Cave and two stalagmites from Glyfada Cave were dated and analyzed for stable oxygen (δ18O) and carbon (δ13C) isotopes. The Glyfada record covers a period from ~78 ka to ~37 ka and shows that the climate in this region responded rapidly to changes in temperatures over Greenland. During Greenland stadial (interstadial) conditions colder (warmer) and drier (wetter) conditions are reflected by depleted (enriched) δ13C-values in the speleothems. The Kapsia record covers a period from ~2900 to ~1100 years BP. A comparison between the modern stalagmite top isotopes and meteorological data shows that a main control on stalagmite δ18O is wet season precipitation amount. The δ18O record from Kapsia indicates cyclical humidity changes of close to 500 years, with rapid shifts toward wetter conditions followed by slowly developing aridity. Superimposed on this signal is a centennial signal of precipitation variability. A second speleothem from Kapsia with multiple horizons of fine sediments from past flood events intercalated with the calcite is used to develop a new, quick and non-destructive method for tracing flood events in speleothems by analyzing a thick section with an XRF core scanner. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Accepted.</p>

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No description available.

Recent drought over West Africa (1970s-present) has been a global concern, and the ability to predict the frequency and severity of future droughts is important to mitigate the devastating socio-economic effects of drought. The Sahel region, situated at 10-20°N just south of the arid Sahara Desert and north of the forested Guinea Coast, is particularly vulnerable to drought periodicity because rainfall is already low at 400 mm yr-1. The ability to predict future climate variability depends on adequate knowledge of fluctuations in the past. In West Africa, meteorological records are too sparse and too short in duration to characterize the drought frequency. Consequently, climate reconstructions from lacustrine sediment records are increasingly recognized as an important source of information on past climate variability. Lake Bosomtwe, Ghana (6o30N and 1o25W) was formed over one million years ago by a meteorite impact crater in the Guinea Coast region, just south of the Sahel region. Lake Bosomtwe has a closed-drainage hydrology and lake levels are known to fluctuate with the net flux in rainfall inputs relative to evaporative outputs. In 2004, the International Continental Scientific Drilling Program recovered the complete sediment record for paleoclimatic reconstructions. However, very little has been studied of the limnological conditions that lead to the formation of laminated sediments in Lake Bosomtwe. This thesis has set out to understand the influence climate has on the physical, chemical and biological in-lake processes that generate sedimenting materials, which are preserved as laminated sediment layers. Two years of water column sampling of temperature, oxygen and nutrients at a central deep-water site (78 m water depth maximum) found that this quiescent crater lake is thermally stratified during much of the year, with anoxia persisting below 35 m water depth. During the short dry season of July and August, the monsoon rains that are associated with the intertropical convergence zone (ITCZ) are displaced northwards over the Sahel region (and away from lake Bosomtwe), and cool air temperatures and clear night skies lead to the disruption of the thermocline and circulation of dissolved nutrients nitrogen (N) and phosphorus (P) in Lake Bosomtwe. Phytoplankton primary productivity, as measured by particulate carbon and chlorophyll a concentrations, was found to increase markedly following the nutrient upwelling event in August. Sediment trap samplers deployed at 20 and 30 m water depth captured the pattern of organic matter deposition and a high flux of organic sediment was deposited shortly after the nutrient upwelling episode in August. The composition of these organic-rich sediments was distinguished by a marked depletion in δ13C and enrichment of δ15N, as compared to sediments deposited before and after this event. Spatial assessment of sediment cores identified that presently, visible laminations were preserved at and below 35 m water depth, but, not at shallower depths. Water depth was also positively correlated with the organic matter content in sediment records and could be used to reconstruct pre-historic lake levels down core. The relationship between lake level and organic content in sediments predicted that water levels were likely 22 m lower than present levels during the period ~1425-1610 CE, which corresponds with a climatic periods known as the Little Ice Age (LIA). The spatial sediment trends also revealed that inorganic sedimentation rates had increased since the onset of recent land clearance and road construction in the catchment, particularly to the north, near the town of Abono. For this reason, two cores from the central deep-water region of Lake Bosomtwe were analysed for organic and carbonate content, δ13C and δ15N, nutrients (C, N, P), magnetic susceptibility, greyscale imagery of the x-radiograph and micro-X-ray analysis of elemental constituents. Paleoenvironmental reconstructions during the past 550 years found that climate-driven lake level change was a prominent factor contributing to the organic content of sediments. High inorganic content, iron concentrations and depleted δ13C distinguished a low stand during the LIA (~1425-1610) when pelagic sediments were likely exposed to periodic oxygenation. High concentrations of organic matter, calcium (Ca) and strontium (Sr), enrichment of δ13C and low C:N ratios were indicative of wet years that likely increased lake levels and the depth of water column mixing. However, sediments with high organic content, depleted δ13C signatures and reduced Ca and Sr concentrations were suggestive of drought years that restricted the depth of seasonal water column mixing and nutrient circulation and did not necessarily result in pronounced lake-level change. During the past century, δ13C of bulk matter was positively correlated with the rainfall anomalies (r2 = 0.45, P < 0.002), indicating that droughts can result in reduced primary productivity, which may ultimately lower fishery yields. The communities living within the crater are dependent on subsistence fishing and farming, and predicting the drought frequency and magnitude in this region is essential to protecting both the ecosystem and the human population. Long-range climate forecasts for West Africa predict greater drought and increasing air temperature. However, with a detailed long-term paleoclimatic reconstruction from Lake Bosomtwe sediment records, potentially the accuracy of these predictions can be improved and better equip policy makers to enact a viable action plan in the best interests of the people.