27 resultados para stable isotopic

em Digital Commons at Florida International University


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Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. ^ High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, δ 15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM δ 15N values ranged on a quarterly basis by 7‰, while δ 13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms. ^

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The relative importance of algal and detrital energy pathways remains a central question in wetlands ecology. We used bulk stable isotope analysis and fatty acid composition to investigate the relative contributions of periphyton (algae) and floc (detritus) in a freshwater wetland with the goal of determining the inputs of these resource pools to lower trophic-level consumers. All animal samples revealed fatty acid markers indicative of both microbial (detrital) and algal origins, though the relative contributions varied among species. Vascular plant markers were in low abundance in most consumers. Detritivory is important for chironomids and amphipods, as demonstrated by the enhanced bacterial fatty acids present in both consumers, while algal resources, in the form of periphyton, likely support ephemeropteran larvae. Invertebrates such as amphipods and grass shrimp appear to be important resources for small omnivorous fish, while Poecilia latipinna appear to strongly use periphyton and Ephemeroptera larvae as food sources. Both P. latipinna and Lepomis spp. assimilated small amounts of vascular plant debris, possibly due to unintentional ingestion of floc while foraging for invertebrates and insect larvae. Physid snails, Haitia spp., were characterized by considerably different fatty acid compositions than other taxa examined, and likely play a unique role in Everglades’ food webs.

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Precipitation data collected from five sites in south Florida indicate a strong seasonal and spatial variation in δ18O and δD, despite the relatively limited geographic coverage and low-lying elevation of each of the collection sites. Based upon the weighted-mean stable isotope values, the sites were classified as coastal Atlantic, inland, and lower Florida Keys. The coastal Atlantic sites had weighted-mean values of δ18O and δD of −2.86‰ and −12.8‰, respectively, and exhibited a seasonal variation with lower δ18O and δD values in the summer wet-season precipitation (δ18O = −3.38‰, δD = −16.5‰) as compared to the winter-time precipitation (δ18O = −1.66‰, δD = −3.2‰). The inland site was characterized as having the highest d-excess value (+13.3‰), signifying a contribution of evaporated Everglades surface water to the local atmospheric moisture. In spite of its lower latitude, the lower Keys site located at Long Key had the lowest weighted-mean stable isotope values (δ18O = −3.64‰, δD = −20.2‰) as well as the lowest d-excess value of (+8.8‰). The lower δD and δ18O values observed at the Long Key site reflect the combined effects of oceanic vapor source, fractionation due to local precipitation, and slower equilibration of the larger raindrops nucleated by a maritime aerosol. Very low δ18O and δD values (δ18O < −6‰, δD < −40‰) were observed just prior to the passage of hurricanes from the Gulf of Mexico as well as during cold fronts from the north-west. These results suggest that an oceanic vapor source region to the west, may be responsible for the extremely low δD and δ18O values observed during some tropical storms and cold fronts.

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Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, ä15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM ä15N values ranged on a quarterly basis by 7‰, while ä13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms.

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Long-term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on Florida Bay biogeochemistry. Planktonic communities respond quickly to changes in water quality, thus spatial variability in community composition and relationships to nutrient parameters must be understood in order to evaluate future downstream impacts of modifications to Everglades hydrology. Here we present initial results combining flow cytometry analyses of phytoplankton and bacterial populations (0.1–50 μm size fraction) with measurements of δ13C and δ15N composition and dissolved inorganic nutrient concentrations to explore proxies for planktonic species assemblage compositions and nutrient cycling. Particulate organic material in the 0.1–50 μm size fraction was collected from five stations in Northeastern and Western Florida Bay to characterize spatial variability in species assemblage and stable isotopic composition. A dense bloom of the picocyanobacterium, Synechococcus elongatus, was observed at Western Florida Bay sites. Smaller Synechococcus sp. were present at Northeast sites in much lower abundance. Bacteria and detrital particles were also more abundant at Western Florida Bay stations than in the northeast region. The highest abundance of detritus occurred at Trout Creek, which receives freshwater discharge from the Everglades through Taylor Slough. In terms of nutrient availability and stable isotopic values, the S. elongatus population in the Western bay corresponded to low DIN (0.5 μM NH 4 + ; 0.2 μM NO 3 − ) concentrations and depleted δ15N signatures ranging from +0.3 to +0.8‰, suggesting that the bloom supported high productivity levels through N2-fixation. δ15N values from the Northeast bay were more enriched (+2.0 to +3.0‰), characteristic of N-recycling. δ13C values were similar for all marine Florida Bay stations, ranging from −17.6 to −14.4‰, however were more depleted at the mangrove ecotone station (−25.5 to −22.3‰). The difference in the isotopic values reflects differences in carbon sources. These findings imply that variations in resource availability and nutrient sources exert significant control over planktonic community composition, which is reflected by stable isotopic signatures.

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Cotton is the most abundant natural fiber in the world. Many countries are involved in the growing, importation, exportation and production of this commodity. Paper documentation claiming geographic origin is the current method employed at U.S. ports for identifying cotton sources and enforcing tariffs. Because customs documentation can be easily falsified, it is necessary to develop a robust method for authenticating or refuting the source of the cotton commodities. This work presents, for the first time, a comprehensive approach to the chemical characterization of unprocessed cotton in order to provide an independent tool to establish geographic origin. Elemental and stable isotope ratio analysis of unprocessed cotton provides a means to increase the ability to distinguish cotton in addition to any physical and morphological examinations that could be, and are currently performed. Elemental analysis has been conducted using LA-ICP-MS, LA-ICP-OES and LIBS in order to offer a direct comparison of the analytical performance of each technique and determine the utility of each technique for this purpose. Multivariate predictive modeling approaches are used to determine the potential of elemental and stable isotopic information to aide in the geographic provenancing of unprocessed cotton of both domestic and foreign origin. These approaches assess the stability of the profiles to temporal and spatial variation to determine the feasibility of this application. This dissertation also evaluates plasma conditions and ablation processes so as to improve the quality of analytical measurements made using atomic emission spectroscopy techniques. These interactions, in LIBS particularly, are assessed to determine any potential simplification of the instrumental design and method development phases. This is accomplished through the analysis of several matrices representing different physical substrates to determine the potential of adopting universal LIBS parameters for 532 nm and 1064 nm LIBS for some important operating parameters. A novel approach to evaluate both ablation processes and plasma conditions using a single measurement was developed and utilized to determine the "useful ablation efficiency" for different materials. The work presented here demonstrates the potential for an a priori prediction of some probable laser parameters important in analytical LIBS measurement.

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Southeast Florida’s continual urban expansion will potentially increase anthropogenic pollution in adjacent coastal marine systems. Furthermore, increased nutrient loads could have detrimental effects on the already threatened Florida Reef Tract. The present study uses a stable isotopic approach to determine the sources and the impact of nutrients on the Florida Reef Tract. δ13C and δ15N analysis of macroalgae, sponges, and sediment were analyzed in order to determine nutrient inputs in this region. While δ13C data did not display any significant trends spatially, δ15N values of the majority of biota exhibited a strong East to West gradient with more enriched values close to shore. Relative enrichment in δ15N values were measured for sediments sampled along the Florida Reef Tract in comparison to a pristine Marquesas Keys sediment core. The δ15N data also implies that shoreline anthropogenic nutrients have more nutrient loading implications on reefs than major point sources.

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Cotton is the most abundant natural fiber in the world. Many countries are involved in the growing, importation, exportation and production of this commodity. Paper documentation claiming geographic origin is the current method employed at U.S. ports for identifying cotton sources and enforcing tariffs. Because customs documentation can be easily falsified, it is necessary to develop a robust method for authenticating or refuting the source of the cotton commodities. This work presents, for the first time, a comprehensive approach to the chemical characterization of unprocessed cotton in order to provide an independent tool to establish geographic origin. Elemental and stable isotope ratio analysis of unprocessed cotton provides a means to increase the ability to distinguish cotton in addition to any physical and morphological examinations that could be, and are currently performed. Elemental analysis has been conducted using LA-ICP-MS, LA-ICP-OES and LIBS in order to offer a direct comparison of the analytical performance of each technique and determine the utility of each technique for this purpose. Multivariate predictive modeling approaches are used to determine the potential of elemental and stable isotopic information to aide in the geographic provenancing of unprocessed cotton of both domestic and foreign origin. These approaches assess the stability of the profiles to temporal and spatial variation to determine the feasibility of this application. This dissertation also evaluates plasma conditions and ablation processes so as to improve the quality of analytical measurements made using atomic emission spectroscopy techniques. These interactions, in LIBS particularly, are assessed to determine any potential simplification of the instrumental design and method development phases. This is accomplished through the analysis of several matrices representing different physical substrates to determine the potential of adopting universal LIBS parameters for 532 nm and 1064 nm LIBS for some important operating parameters. A novel approach to evaluate both ablation processes and plasma conditions using a single measurement was developed and utilized to determine the “useful ablation efficiency” for different materials. The work presented here demonstrates the potential for an a priori prediction of some probable laser parameters important in analytical LIBS measurement.

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In the Florida Everglades, tree islands are conspicuous heterogeneous elements in a complex wetland landscape. I investigated the effects of increased freshwater flow in southern Everglades seasonally flooded tree islands, and characterized biogeochemical interactions among tree islands and the marsh landscape matrix, specifically examining hydrologic flows of nitrogen (N), and landscape N sequestration capacity. I utilized ecological trajectories of key ecosystem variables to differentiate effects of increased sheetflow and hydroperiod. I utilized stable isotope analyses and nutrient content of tree island ecosystem components to test the hypothesis that key processes in tree island nitrogen cycling would favor ecosystem N sequestration. I combined estimates of tree island ecosystem N standing stocks and fluxes, soil and litter N transformation rates, and hydrologic inputs of N to quantify the net sequestration of N by a seasonally flooded tree island. ^ Results show that increased freshwater flow to seasonally flooded tree islands promoted ecosystem oligotrophy, whereas reduced flows allowed some plant species to cycle P less efficiently. As oligotrophy is a defining parameter of Everglades wetlands, and likely promotes belowground production and peat development, reintroducing freshwater flow from an upstream canal had a favorable effect on ecosystem dynamics of tree islands in the study area. Important factors influencing the stable isotopic composition of nitrogen and carbon were: (1) a contribution to soil N by soil invertebrates, animal excrement, and microbes, (2) a possible NO3 source from an upstream canal and an "open" ecosystem N cycle, and (3) greater availability of phosphorus in tree islands relative to the marsh landscape, suggesting that tree island N cycling favors N sequestration. Hydrologic sources of N were dominated by surface water loads of NO3- and NH 4+, and an important soil N transformation promoting the net loss of surface water DIN was nitrate immobilization associated with soils and surficial leaf litter. The net inorganic N sequestration capacity of a seasonally flooded tree island was 50 g yr-1 m -2. Thus, tree islands likely have an important function in landscape sequestration of inorganic N, and may reduce significant anthropogenic N loads to downstream coastal systems. ^

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The Everglades are undergoing the world largest wetland restoration project with the aim of returning this system to hydrological conditions in place prior to anthropogenic modifications. Therefore, it is essential to know what these pristine conditions were. In this work, molecular marker (biomarker) distributions and carbon stable isotopic signatures in sediment samples were employed to assess historical environmental changes in Florida Bay over approximately the last 4000 years. Two biomarkers of terrestrial plants, particularly for mangroves (taraxerol and C29 n-alkane), combined with two seagrass proxies (the Paq and the C25/C 27 n-alkan-2-one ratio) revealed a sedimentary environmental shift from freshwater marshes to mangrove swamps and then to seagrass dominated marine ecosystems, likely as a result of sea-level rise in Florida Bay since the Holocene. The maximum values for the Paq and the C 25/C27 n-alkan-2-ones occurred during the 20th century, suggesting that the greatest abundance of seagrass cover is a recent rather than a historical, long-term phenomenon. The greater oscillation in frequency and amplitude for the biomarkers after 1900 potentially reflects an ecosystem under increasing anthropogenic stress. Several algal biomarkers such as C20 highly branched isoprenoids (HBIs), C 25 HBIs and dinosterol indicative of cyanobacteria, diatom and dinoflagellate organic matter inputs respectively, increased dramatically in the latter part of the 20th century and were attributed to recent anthropogenic changes in Florida Bay. ^ The highlight of this work is the development of HBIs as paleo-proxies. As biomarkers of diatoms, the C25 HBIs in the core from the central bay displayed the highest concentration at mid depth, reflecting strong historical inputs of diatom-derived sedimentary OM during that period. In fact, the depth profile of C25 HBIs coincided quite well with historical variations in diatom abundance and variations in diatom species composition in central Florida Bay based on the results of fossil diatom species analysis by microscopy. This study provides evidence that some C25 HBIs can be applied as biomarkers for certain diatom inputs in paleoenvironmental studies. The sources of C20 and C30 HBIs and their potential applicability as paleo-proxies were also investigated and their sources assessed based on their δ13C distributions. ^

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Worldwide declines in populations of large elasmobranchs and the potential cascading effects on marine ecosystems have garnered considerable attention. Far less appreciated are the potential ecological impacts of changes in abundances of small to medium bodied elasmobranchs mesopredators. Crucial to elucidating the role of these elasmobranchs is an understanding of their habitat use and foraging ecology in pristine conditions. I investigated the trophic interactions and factors driving spatiotemporal variation in abundances of elasmobranch mesopredators in the relatively pristine ecosystem of Shark Bay, Australia. First, I describe the species composition and seasonal habitat use patterns of elasmobranch mesopredator on the sandflats of Shark Bay. Juvenile batoids dominated this diverse community and were extremely abundant in nearshore microhabitats during the warm season. Stomach content analysis and stable isotopic analysis revealed that there is a large degree of dietary overlap between common batoid species. Crustaceans, which tend to be found in seagrass habitats, dominated diets. Despite isotopic differences between many species, overlap in isotopic niche space was high and there was some degree of individual specialization. I then, investigated the importance of abiotic (temperature and water depth) and biotic (prey and predator abundance) factors in shaping batoid habitat use. Batoids were most abundant and tended to rest in shallow nearshore waters when temperatures were high. This pattern coincides with periods of large shark abundance suggesting batoids were seeking refuge from predators rather than selecting optimal temperatures. Finally, I used acoustic telemetry to examine batoid residency and diel use of the sandflats. Individual batoids were present on the sandflats during both the warm and cold seasons and throughout the diel cycle, suggesting lower sandflat densities during the cold season were a result of habitat shifts rather than migration out of Shark Bay. Combined, habitat use and dietary results suggest that batoids have the potential to seasonally impact sandflat dynamics through their presence, although foraging may be limited on the sandflats. Interestingly, my results suggest that elasmobranch mesopredators in pristine ecosystems probably are not regulated by food supply and their habitat use patterns and perhaps ecosystem impacts may be influenced by their predators.

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1. Highly mobile top predators are hypothesized to spatially and/or temporally link disparate habitats through the combination of their movement and feeding patterns, but recent studies suggest that individual specialization in habitat use and feeding could keep habitats compartmentalized. 2.  We used passive acoustic telemetry and stable isotope analysis to investigate whether specialization in movement and feeding patterns of American alligators (Alligator mississippiensis) in an oligotrophic subtropical estuary created habitat linkages between marine and estuarine/freshwater food webs. 3.  Individual alligators adopted one of the three relatively distinct movement tactics that were linked to variation in diets. Fifty-six per cent of alligators regularly travelled from the upstream (freshwater/mid-estuary) areas into the downstream (marine-influenced) areas where salinities exceed those typically tolerated by alligators. Thirty-one per cent of the alligators made regular trips from the mid-estuarine habitat into the upstream habitat; 13% remained in the mid-estuary zone year-round. 4.  Stable isotopic analysis indicated that, unlike individuals remaining in the mid-estuary and upstream zones, alligators that used the downstream zone fed at least partially from marine food webs and likely moved to access higher prey abundance at the expense of salt stress. Therefore, ‘commuting’ alligators may link marine food webs with those of the estuary and marshes in the coastal Everglades and create an upstream vector for allochthonous nutrient inputs into the estuary. 5.  This study lends further support to the hypothesis that large-bodied highly mobile predators faced with trade-offs are likely to exhibit individual specialization leading to habitat linkages, rather than compartmentalization. However, the conditions under which this scenario occurs require further investigation.

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Trophic downgrading of ecosystems necessitates a functional understanding of trophic cascades. Identifying the presence of cascades, and the mechanisms through which they occur, is particularly important for seagrass meadows, which are among the most threatened ecosystems on Earth. Shark Bay, Western Australia provides a model system to investigate the potential importance of top-down effects in a relatively pristine seagrass ecosystem. The role of megagrazers in the Shark Bay system has been previously investigated, but the role of macrograzers (i.e., teleosts), and their importance relative to megagrazers, remains unknown. The objective of my dissertation was to elucidate the importance of teleost macrograzers in transmitting top-down effects in seagrass ecosystems. Seagrasses and macroalgae were the main food of the abundant teleost Pelates octolineatus, but stable isotopic values suggested that algae may contribute a larger portion of assimilated food than suggested by gut contents. Pelates octolineatus is at risk from numerous predators, with pied cormorants (Phalacrocorax varius) taking the majority of tethered P. octolineatus. Using a combination of fish trapping and unbaited underwater video surveillance, I found that the relative abundance of P. octolineatus was greater in interior areas of seagrass banks during the cold season, and that the mean length of P. octolineatus was greater in these areas compared to along edges of banks. Finally, I used seagrass transplants and exclosure experiments to determine the relative effect of megagrazers and macrograzers on the establishment and persistence of three species of seagrasses in interior microhabitats. Teleost grazing had the largest impact on seagrass species with the highest nutrient content, and these impacts were primarily observed during the warm season. My findings are consistent with predictions of a behaviorally-mediated trophic cascade initiated by tiger sharks (Galeocerdo cuvier) and transmitted through herbivorous fishes and their predators.

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Trophic downgrading of ecosystems necessitates a functional understanding of trophic cascades. Identifying the presence of cascades, and the mechanisms through which they occur, is particularly important for seagrass meadows, which are among the most threatened ecosystems on Earth. Shark Bay, Western Australia provides a model system to investigate the potential importance of top-down effects in a relatively pristine seagrass ecosystem. The role of megagrazers in the Shark Bay system has been previously investigated, but the role of macrograzers (i.e., teleosts), and their importance relative to megagrazers, remains unknown. The objective of my dissertation was to elucidate the importance of teleost macrograzers in transmitting top-down effects in seagrass ecosystems. Seagrasses and macroalgae were the main food of the abundant teleost Pelates octolineatus, but stable isotopic values suggested that algae may contribute a larger portion of assimilated food than suggested by gut contents. Pelates octolineatus is at risk from numerous predators, with pied cormorants (Phalacrocorax varius) taking the majority of tethered P. octolineatus. Using a combination of fish trapping and unbaited underwater video surveillance, I found that the relative abundance of P. octolineatus was greater in interior areas of seagrass banks during the cold season, and that the mean length of P. octolineatus was greater in these areas compared to along edges of banks. Finally, I used seagrass transplants and exclosure experiments to determine the relative effect of megagrazers and macrograzers on the establishment and persistence of three species of seagrasses in interior microhabitats. Teleost grazing had the largest impact on seagrass species with the highest nutrient content, and these impacts were primarily observed during the warm season. My findings are consistent with predictions of a behaviorally-mediated trophic cascade initiated by tiger sharks (Galeocerdo cuvier) and transmitted through herbivorous fishes and their predators.

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Stable isotopes are important tools for understanding the trophic roles of elasmobranchs. However, whether different tissues provide consistent stable isotope values within an individual are largely unknown. To address this, the relationships among carbon and nitrogen isotope values were quantified for blood, muscle, and fin from juvenile bull sharks (Carcharhinus leucas) and blood and fin from large tiger sharks (Galeocerdo cuvier) collected in two different ecosystems. We also investigated the relationship between shark size and the magnitude of differences in isotopic values between tissues. Isotope values were significantly positively correlated for all paired tissue comparisons, but R2 values were much higher for δ13C than for δ15N. Paired differences between isotopic values of tissues were relatively small but varied significantly with shark total length, suggesting that shark size can be an important factor influencing the magnitude of differences in isotope values of different tissues. For studies of juvenile sharks, care should be taken in using slow turnover tissues like muscle and fin, because they may retain a maternal signature for an extended time. Although correlations were relatively strong, results suggest that correction factors should be generated for the desired study species and may only allow coarse-scale comparisons between studies using different tissue types.