Upwelling, atmospheric nitrogen (N2) fixation by cyanobacteria, and freshwater inputs from the Mississippi River system have been shown to stimulate new production by alleviating nitrogen (N) limitation in the northern Gulf of Mexico (GoM). Stable carbon (delta13C) and nitrogen (delta15N) isotopes were used to investigate whether these sources are utilized differentially by coastal and marine pelagic food webs. Particulate organic matter (POM), Trichodesmium, and zooplankton were collected from the Mississippi River plume and Loop Current (LC) which were detected using remote sensing data. Stable isotope values were used to separate coastal and marine water masses and environmental data (salinity, nutrient and pigment concentrations) allowed me to relate variability to the degree of freshwater influence. Published food web data from these two environments were then assessed to establish whether isotopic baseline shifts observed in our data occur at an ecosystem level. Isotope values of the POM and zooplankton were found to be significantly different between coastal and marine water masses. This was not the case for Trichodesmium whose isotope values were not significantly different between the two water masses. We found that marine water masses (sal > 35) exhibited silicate concentrations, cyanobacterial pigments and DIN: P that suggest an increased abundance of diazotrophs. In contrast, coastal water masses (sal < 35) exhibited increased diatom pigments and molar C:N indicating terrestrial sources fuel phytoplankton production. When published food web data were compared, we found producer and consumer delta15N values were enriched in the coastal compared to the marine environments. This work suggests that differences in delta15N values within my data set and published data reflect a shift in the use of biologically available N where higher trophic levels are sustained by diazotrophic activity in marine environments versus those supported by terrestrial sources in coastal ones. Food webs that have been constructed without considering Trichodesmium as a significant source of organic matter in the GoM should be reconsidered. By re-evaluating published data, this research gives insight into the early life ecology of larval fishes and works to help answer questions about the structure and function of pelagic food webs.

The blue crab, Callinectes sapidus, supports a successful fishery in the Atlantic Ocean and throughout the Gulf of Mexico, with a total landing of 8,158,788 lb. and a total value of $10,562,128 for the state of Florida during 2012 (FWC 2012 Annual Landings Summary). An accurate and comprehensive understanding of the blue crab's life history and seasonal migration behavior is essential in defining effective management strategies for the fishery. Tag recapture studies and ultrasonic tracking methods for studying blue crab migrations are costly in terms of time and resources. In this study an alternative approach, microchemical natural tagging, was successfully used to determine a female's mating habitat. This approach assumes that the exoskeleton of the post-terminal molt female blue crab reflects the mating habitat's chemical signature and that the chemical signals are stable over time. To test these hypotheses, mature female blue crabs were collected from two Tampa Bay locations. Collected crabs were placed in tanks for 29 days, a subset was sacrificed at T = 0 and then twice per week, and the exoskeletons were analyzed via Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Elemental Analyzer Infrared Mass Spectrometry (EA-IRMS) to observe the stability of the exoskseletal chemical signature over time. Over the 29 day time series, no significant change in the concentrations of Li, Ca, and Ba, or the isotopic ratios of 13C/12C (δ13C) and 15N/14N (δ15N) were observed (ANOVA p-value > 0.05). A Canonical Analysis of Principal Coordinates (CAP)-based discriminate analysis with leave-one-out cross-validation collectively compared Li concentrations, δ13C, and δ15N among five Tampa Bay locations, producing a confusion matrix successfully classifying field collected crabs into: Alafia River 33%#37;, Little Manatee River 71%#37;, Palm River 67%#37;, Safety Harbor 30%#37;, and Skyway Fishing Pier 83%#37;, with an overall classification success of 66%#37;. These results suggest that the largest biomass component of the migratory pulse collected near the mouth of Tampa Bay was dominated by crabs originating from an area not widely harvested by commercial fishermen, as relatively few of the migrating females were matched to riverine locations that were intensively fished. Instead, most appeared to originate from open waters of Tampa Bay. It is possible that low densities of blue crab inhabiting a large area that is not commercially fished, effectively shields a proportion of the individuals in the Tampa Bay estuary from economic exploitation, creating a density-dependent natural harvest refugium.

Feeding ecology and trophic interactions of six species of wading birds were explored through a combined analysis of stable isotope profiles and endoparasite communities. Stable isotopes broadly characterize the feeding preferences and geographic information, while parasite communities reflect long-term trends in feeding ecology. Deceased birds were obtained from four South Florida wildlife rehabilitation organizations. Of the 81 birds dissected, 73 contained parasites. Parasites were predominately found within the gastrointestinal tract. Host and range extensions were noted for several parasite taxa. Bird host species had a significant effect on the parasite community (P=0.001) while wildlife center location and maturity status did not. Stable nitrogen (δ15N) values for pectoral muscle tissues, representing approximately 24 days, ranged from 6.44 to 13.48‰ while stable carbon (δ13C) values ranged from -33.39 to -11.66‰. δ13C varied significantly among location (P=0.0002) and δ15N varied significantly among species (P15N and δ13C was analyzed in combination; bird species (P=0.001) and location (P=0.001) were significantly different. By using this combined approach of stable isotope analysis and parasite identification, it was possible to elucidate more components of bird feeding ecology. Stable isotope analysis provided knowledge on trophic interactions based on δ15N values, while δ13C was used to determine the differences in geographic foraging location. As endoparasites are acquired trophically via food-web interactions, identifying the parasite community allowed for trophic links to be drawn between organisms present within the same environment. Combining these two techniques allows for an abundance of information on feeding ecology and trophic interactions to be obtained.

The Hirnantian mass extinction was the second largest of the Phanerozoic. A global sea level fall resulting from a glaciation on Gondwanaland caused significant changes in ocean circulation patterns and nutrient cycling that is recorded as a worldwide positive δ13C excursion.<p> In chapter 2, carbon and nitrogen isotope profiles were reconstructed from two North American carbonate platforms in Nevada and one in the Yukon with the purpose of gaining a better understanding of proximal to proximal gradients in δ13C values from Hirnantian epeiric seaway sediment. Positive δ13C excursions are recorded in bulk inorganic and organic carbon fractions from all three sections, and in graptolite periderms from one section. A larger positive excursion is recorded in the proximal sediment (7) compared to proximal sediment (3-4). This gradient appears to reflect differences in surface water dissolved inorganic carbon δ13C values across epeiric seas. These findings are consistent with the carbonate weathering hypothesis, that predicts larger positive δ13C shifts in proximal settings of tropical epeiric seas resulting from changes in the local carbon weathering flux caused by the exposure of vast areas of carbonate sediment during glacioeustatic sea level fall and restricted shelf circulation. A 2 positive excursion in δ15N is interpreted to result from increased ocean ventilation, greater partitioning of atmospheric oxygen into downwelling surface waters, oxygen minimum zone shrinkage, and declining denitrification rates. This allowed for upwelling of recycled nitrogen with high 15N values into the photic zone that forced exported organic matter from the photic zone to higher 15N values, consistent with the observed positive shift in 15N during the Hirnantian glaciation. This study presents a conceptual model to explain secular changes in δ13C and δ15N during the transition from a greenhouse to icehouse climate.<p> The second focus of this research, presented in chapter 3, was on improving the chemical and analytical methods for δ18O analysis of biogenic apatites. The technique applies cation exchange chromatography that allows for small sample sizes of apatite (200 µg) to be used for chemical conversion to Ag3PO4. The precision (0.15, 1) of δ18O analysis obtained using a Thermal Conversion Elemental Analyser Continuous Flow Isotope Ratio Mass Spectrometer (TC/EA CF-IRMS), and the ability to collect multipe isotopes (O, Ca, Sr, REE) using a cation exchange column, makes this technique valuable for high-resolution, multi-isotope studies of biogenic apatites.

The Hirnantian mass extinction was the second largest of the Phanerozoic. A global sea level fall resulting from a glaciation on Gondwanaland caused significant changes in ocean circulation patterns and nutrient cycling that is recorded as a worldwide positive δ13C excursion.<p> In chapter 2, carbon and nitrogen isotope profiles were reconstructed from two North American carbonate platforms in Nevada and one in the Yukon with the purpose of gaining a better understanding of proximal to proximal gradients in δ13C values from Hirnantian epeiric seaway sediment. Positive δ13C excursions are recorded in bulk inorganic and organic carbon fractions from all three sections, and in graptolite periderms from one section. A larger positive excursion is recorded in the proximal sediment (7) compared to proximal sediment (3-4). This gradient appears to reflect differences in surface water dissolved inorganic carbon δ13C values across epeiric seas. These findings are consistent with the carbonate weathering hypothesis, that predicts larger positive δ13C shifts in proximal settings of tropical epeiric seas resulting from changes in the local carbon weathering flux caused by the exposure of vast areas of carbonate sediment during glacioeustatic sea level fall and restricted shelf circulation. A 2 positive excursion in δ15N is interpreted to result from increased ocean ventilation, greater partitioning of atmospheric oxygen into downwelling surface waters, oxygen minimum zone shrinkage, and declining denitrification rates. This allowed for upwelling of recycled nitrogen with high 15N values into the photic zone that forced exported organic matter from the photic zone to higher 15N values, consistent with the observed positive shift in 15N during the Hirnantian glaciation. This study presents a conceptual model to explain secular changes in δ13C and δ15N during the transition from a greenhouse to icehouse climate.<p> The second focus of this research, presented in chapter 3, was on improving the chemical and analytical methods for δ18O analysis of biogenic apatites. The technique applies cation exchange chromatography that allows for small sample sizes of apatite (200 µg) to be used for chemical conversion to Ag3PO4. The precision (0.15, 1) of δ18O analysis obtained using a Thermal Conversion Elemental Analyser Continuous Flow Isotope Ratio Mass Spectrometer (TC/EA CF-IRMS), and the ability to collect multipe isotopes (O, Ca, Sr, REE) using a cation exchange column, makes this technique valuable for high-resolution, multi-isotope studies of biogenic apatites.

Water is a valuable and crucial resource, the protection of which poses environmental, social and economic challenges. Fundamental to the sustainable use of water is effective management. In the Canterbury region of New Zealand, nitrate contamination has become a resource management issue due to changes in land use and intensification, which have placed pressure on the region’s groundwater and surface water systems. The purpose of this study was to assess and track nitrate concentrations on the Central Canterbury Plains with specific emphasis on a local point source of nitrate, the Ashburton Meat Processors plant. To make this assessment review of historical data was followed by the collection of 131 groundwater and 25 surface water samples to analyse the geochemical properties of the water and the stable isotopic composition of nitrate in the water. It was hypothesised that nitrate concentrations at a regional scale have increased since regular records began and that the stable isotopic composition of different nitrate sources are not discernable. Nitrate concentrations across the Canterbury region were found to have increased, prompting concerns about water quality. Concentrations are elevated above natural background levels across much of the Canterbury Plains and extreme concentrations are associated with local point sources of nitrate. Nitrate concentrations down gradient of the Ashburton Meat Processing plant are shown to have declined approximately 5% per year for the past ten years, which is in contrast to the rest of the region, where average concentrations have nearly doubled in 20 years. The reduction of contamination from the point source is most likely the result of the implementation of better wastewater management practices in the early 21st century. The δ18O and δ15N values of nitrate were found to be relatively homogenous over the Canterbury Plains. Therefore, it is suggested by this study that the dual-isotope approach alone, is not a viable tool for nitrate source identification in the region. The uniform nitrate stable isotopic composition in Canterbury could be attributed to a single, principle source of nitrate, such as clover, that overprints other isotopic compositions of nitrate source, or may also be the result of soil processes and the farming techniques used in the region. This research presents important findings for the future of identifying and managing nitrate sources in the Canterbury region. Better management practices are required for the diffuse source(s) of nitrate contributing to the widespread contamination. Critical thinking and the willingness of stakeholders to engage in the identifying, documenting and solving problems is necessary to ensure the effective management and sustainability of this precious resource.

Biological and physical sampling of a 10km long, east-west transect was performed during 2007, off the coast of southeast Florida. Temperature and salinity measurements were recorded using a conductivity-temperature-depth (CTD) sensor, and current direction and magnitude measurements were recorded using an acoustic Doppler current profiler (ADCP). Zooplankton samples were collected, during the daytime, using a Tucker multiple net mid-water trawl, with 760μm mesh, at intended depths of ~25m and ~200m, at three stations along the transect. Laboratory analysis indicated that several currents and water masses influenced the density distribution of calanoid copepods and chaetognaths. During April and September 2007, a Subsurface Counter Current existed in conjunction with an offshore meander of the Florida Current. Physical data confirmed the presence of Continental Edge Water and Yucatan Water occupying different spatial and temporal scales, and the boundary between these two water masses existed as the western boundary of the Florida Current. Temperature and salinity profiles confirmed that the Subsurface Counter Current was composed of Continental Edge Water and not Yucatan Water. Therefore, the Subsurface Counter Current observed during the transect was not a cross section of a passing eddy caused by the meandering front of the Florida Current. Densities of both taxa were highest in the Subsurface Counter Current and the Intermediate water, while the lowest densities are found in the Florida Current. Calanoid copepod and chaetognath densities exhibited typical zooplankton trends for tropical and subtropical coastal waters. Densities were highly influenced by the physical parameters of each month. Highest densities were observed in April and the lowest in July/September, typically the nutrient limited season. Analysis by location showed that the calanoid copepod and chaetognath densities were highest inshore and decreased offshore. The Florida Current exhibited the lowest densities for both taxa, while the Subsurface Counter Current and Intermediate water had higher densities. Previously documented southward flow had been associated with an offshore meander of the Florida Current, but during May and July there was a Subsurface Counter Current and an onshore meander of the Florida Current. Densities of both taxa were still lowest in the Florida Current. The stable isotope values of the zooplankton were skewed because of the preservation media and it was not possible to determine if the currents and water masses were isotopically different, and thus creation of a correction factor for the preservation effect was not possible. The δ13C values were variable in magnitude and direction from the control for each taxon. The δ15N values were less variable, but increased from the control, rather than decrease, as was expected for each taxon.

The endangered Hawaiian monk seal has been undergoing dramatic population declines for several decades. These declines may be linked to food resources or environmental changes and this is reflected in the stable isotope analysis of the monk seals. The use of stable carbon (δ13C) and nitrogen (δ15N) isotope ratios on Hawaiian monk seal bone collagen samples collected from 1912 through 2006 determined that changes within the environment and food web of the Hawaiian monk seal may be factors contributing to the decrease in the population. Over the ninety-four year period the overall δ15N of the monk seals was depleted by approximately 3‰ and the δ13C had minimal changes. Monk seals located within the northern extent of the NWHI exhibited the most dramatic changes in stable isotopes. From 1923 through 2006 the δ15N of the Hawaiian monk seals within this area was depleted nearly 6‰, while δ13C was enriched by 2‰. This significant depletion in δ15N, along with the enrichment within the δ13C for the northern NWHI could be caused by an increase in the primary productivity within the area, leading to a shorter food web. This inverse relationship within the northern NWHI could also be a representation of the monk seals foraging more on benthic rather than pelagic prey, or foraging inshore rather than offshore in this region. This northern region was in contrast to the Central and southern islands within the NWHI. The central NWHI seals had nominal change in their δ15N and δ13C from 1912 to 2006; whereas, the southern NWHI seals exhibited a 3.5‰ depletion in δ15N and a nearly 1‰ depletion in δ13C over the span from 1951 through 2006. Within the central NWHI the juvenile monk seals were more depleted in δ15N as compared to the adult monk seals, which could indicate a prey base change for these seals. Within the southern NWHI there was a significant difference within δ15N and δ13C over the decades of the study which could indicate a decrease in the regional productivity. The adult monk seals within the southern region also had an increase in δ15N which could be a indicator of starvation for the seals within this region. Stable carbon and nitrogen isotopes indicate modern monk seals (2000-2006) foraged on a number of different teleost, crustacean, eel, and cephalopod species, correlating to earlier and current studies being conducted on the food sources of the Hawaiian monk seal.

Seagrass habitats are highly productive ecosystems that support marine food webs and provide essential habitat for a variety of species. Seagrass coverages are declining in abundance worldwide. For southeastern Florida in particular, one of the main causes of the decline is disturbance from dredging and removal of substrate. Seagrass beds at three locations in the vicinity of Port Everglades, Florida were assessed for their trophic contribution to the marine organisms in the area. Seagrasses, algae, invertebrates, and vertebrates from the beds were identified and analyzed for stable carbon and nitrogen isotope ratios to determine their contribution as a food source. Significant differences were found in both δ13C and δ15N between both seagrass species and among the three sites. The δ13C of Johnson’s seagrass Halophila johnsonii ranged from -16.28 to -11.27‰ while shoal grass Halodule wrightii ranged from -15.78 to -13.36‰. The δ15N for H. wrightii were more constrained than those of H. johnsonii, 4.69 to 7.08‰ versus 0.80 to 7.86‰, respectively. Neither seagrass species appeared to be a dominant food source for marine organisms at all three study sites. However, the δ13C and δ15N of both seagrass species, Halophila johnsonii and Halodule wrightii, did fall in the fractionation range of potential consumers, -28.78 to -17.11‰ and 1.96 to 12.63‰, indicating that these animals could be ingesting pieces of seagrass while grazing on epiphytes and other primary producers in the area. Epiphytes found on the seagrass blades appeared to be a greater trophic contributor to local organisms. So while the seagrass species in question may not have been major contributors to the diet of many of the local consumers, the seagrasses nontheless played a vital role as habitat for the epiphytes that did serve as a trophic resource in these communities.

This study found evidence of intermittent, multi-year residency periods in northern fur seals (Callorhinus ursinus) using stable isotope ratios in vibrissae and canine teeth. Northern fur seals migrate from the Bering Sea during summer months to lower latitudes and slightly warmer waters of the northeastern Pacific Ocean and California Current in the winter. To determine the length of time spent away from the Bering Sea, growth rate was estimated using the covarying oscillations δ13C and δ15N, estimated to be 0.09 mm/day. The δ13C and δ15N in vibrissae from 30 male fur seals showed a minimum of 13 separate periods of stable covariance covering 3.25+ cm, indicating at least 1 year in warmer, less productive waters of the northeastern Pacific Ocean. The vibrissae isotope ratios were used in conjunction with δ18O from tooth dentin growth layer groups of 20 male northern fur seals; they showed significant enrichment in δ18O in 50% of the animals at age 1-2 years, which indicates extended periods of time spent in lower latitudes in the North Pacific Ocean as δ18O is typically enriched in warmer, less productive waters. Significant changes in δ18O were found to be ~ 0.2‰ enrichment per 10º south latitude, while longitude was found to have 0.2‰ enrichment per 50˚ East longitude. These data show that latitudinal changes, those related to the southerly migration from the Bering Sea to the northeastern Pacific Ocean, are a stronger factor in the shifts in dentinal δ18O than longitudinal shifts. These intermittent periods of occupation are important when estimating population abundance of northern fur seals, especially pups and juveniles.