Mercury isotopic evidence for the importance of particles as a source of mercury to marine organisms.

The origin of methylmercury in pelagic fish remains unclear, with many unanswered questions regarding the production and degradation of this neurotoxin in the water column. We used mercury (Hg) stable isotope ratios of marine particles and biota to elucidate the cycling of methylmercury prior to incorporation into the marine food web. The Hg isotopic composition of particles, zooplankton, and fish reveals preferential methylation of Hg within small (< 53 µm) marine particles in the upper 400 m of the North Pacific Ocean. Mass-dependent Hg isotope ratios (δ202Hg) recorded in small particles overlap with previously estimated δ202Hg values for methylmercury sources to Pacific and Atlantic Ocean food webs. Particulate compound specific isotope analysis of amino acids (CSIA-AA) yield δ15N values that indicate more-significant microbial decomposition in small particles compared to larger particles. CSIA-AA and Hg isotope data also suggest that large particles (> 53 µm) collected in the equatorial ocean are distinct from small particles and resemble fecal pellets. Additional evidence for Hg methylation within small particles is provided by a statistical mixing model of even mass-independent (Δ200Hg and Δ204Hg) isotope values, which demonstrates that Hg within near-surface marine organisms (0-150 m) originates from a combination of rainfall and marine particles. In contrast, in meso- and upper bathypelagic organisms (200-1,400 m), the majority of Hg originates from marine particles with little input from wet deposition. The occurrence of methylation within marine particles is supported further by a correlation between Δ200Hg and Δ199Hg values, demonstrating greater overlap in the Hg isotopic composition of marine organisms with marine particles than with total gaseous Hg or wet deposition.

Mercury isotopes identify near-surface marine mercury in deep-sea trench biota.

Mercury isotopic compositions of amphipods and snailfish from deep-sea trenches reveal information on the sources and transformations of mercury in the deep oceans. Evidence for methyl-mercury subjected to photochemical degradation in the photic zone is provided by odd-mass independent isotope values (Δ199Hg) in amphipods from the Kermadec Trench, which average 1.57‰ (±0.14, n = 12, SD), and amphipods from the Mariana Trench, which average 1.49‰ (±0.28, n = 13). These values are close to the average value of 1.48‰ (±0.34, n = 10) for methyl-mercury in fish that feed at ∼500-m depth in the central Pacific Ocean. Evidence for variable contributions of mercury from rainfall is provided by even-mass independent isotope values (Δ200Hg) in amphipods that average 0.03‰ (±0.02, n = 12) for the Kermadec and 0.07‰ (±0.01, n = 13) for the Mariana Trench compared to the rainfall average of 0.13 (±0.05, n = 8) in the central Pacific. Mass-dependent isotope values (δ202Hg) are elevated in amphipods from the Kermadec Trench (0.91 ±0.22‰, n = 12) compared to the Mariana Trench (0.26 ±0.23‰, n = 13), suggesting a higher level of microbial demethylation of the methyl-mercury pool before incorporation into the base of the foodweb. Our study suggests that mercury in the marine foodweb at ∼500 m, which is predominantly anthropogenic, is transported to deep-sea trenches primarily in carrion, and then incorporated into hadal (6,000-11,000-m) food webs. Anthropogenic Hg added to the surface ocean is, therefore, expected to be rapidly transported to the deepest reaches of the oceans.

Amino acid δ13C and δ15N analyses reveal distinct species-specific patterns of trophic plasticity in a marine symbiosis.

Compound-specific isotope analyses (CSIA) and multivariate "isotope fingerprinting" track biosynthetic sources and reveal trophic interactions in food webs. However, CSIA have not been widely applied in the study of marine symbioses. Here, we exposed a reef coral (Montipora capitata) in symbiosis with Symbiodiniaceae algae to experimental treatments (autotrophy, mixotrophy, heterotrophy) to test for trophic shifts and amino acid (AA) sources using paired bulk (δ13C, δ15N) and AA-CSIA (δ13CAA, δ15NAA). Treatments did not influence carbon or nitrogen trophic proxies, thereby not supporting nutritional plasticity. Instead, hosts and symbionts consistently overlapped in essential- and nonessential-δ13CAA (11 of 13 amino acids) and trophic- and source-δ15NAA values (9 of 13 amino acids). Host and symbiont trophic-δ15NAA values positively correlated with a plankton end-member, indicative of trophic connections and dietary sources for trophic-AA nitrogen. However, mass balance of AA-trophic positions (TPGlx-Phe) revealed heterotrophic influences to be highly variable (1-41% heterotrophy). Linear discriminant analysis using M. capitata mean-normalized essential-δ13CAA with previously published values (Pocillopora meandrina) showed similar nutrition isotope fingerprints (Symbiodiniaceae vs. plankton) but revealed species-specific trophic strategies. Montipora capitata and Symbiodiniaceae shared identical AA-fingerprints, whereas P. meandrina was assigned to either symbiont or plankton nutrition. Thus, M. capitata was 100% reliant on symbionts for essential-δ13CAA and demonstrated autotrophic fidelity and contrasts with trophic plasticity reported in P. meandrina. While M. capitata AA may originate from host and/or symbiont biosynthesis, AA carbon is Symbiodiniaceae-derived. Together, AA-CSIA/isotope fingerprinting advances the study of coral trophic plasticity and are powerful tools in the study of marine symbioses.

Trophic Ecology of the Tropical Pacific Sponge Mycale grandis Inferred from Amino Acid Compound-Specific Isotopic Analyses.

Many sponges host abundant and active microbial communities that may play a role in the uptake of dissolved organic matter (DOM) by the sponge holobiont, although the mechanism of DOM uptake and metabolism is uncertain. Bulk and compound-specific isotopic analysis of whole sponge, isolated sponge cells, and isolated symbiotic microbial cells of the shallow water tropical Pacific sponge Mycale grandis were used to elucidate the trophic relationships between the host sponge and its associated microbial community. δ15N and δ13C values of amino acids in M. grandis isolated sponge cells are not different from those of its bacterial symbionts. Consequently, there is no difference in trophic position of the sponge and its symbiotic microbes indicating that M. grandis sponge cell isolates do not display amino acid isotopic characteristics typical of metazoan feeding. Furthermore, both the isolated microbial and sponge cell fractions were characterized by a similarly high ΣV value-a measure of bacterial-re-synthesis of organic matter calculated from the sum of variance among individual δ15N values of trophic amino acids. These high ΣV values observed in the sponge suggest that M. grandis is not reliant on translocated photosynthate from photosymbionts or feeding on water column picoplankton, but obtains nutrition through the uptake of amino acids of bacterial origin. Our results suggest that direct assimilation of bacterially synthesized amino acids from its symbionts, either in a manner similar to translocation observed in the coral holobiont or through phagotrophic feeding, is an important if not primary pathway of amino acid acquisition for M. grandis.

Effects of chemical preservation on bulk and amino acid isotope ratios of zooplankton, fish, and squid tissues.

RATIONALE: It is imperative to understand how chemical preservation alters tissue isotopic compositions before using historical samples in ecological studies. Specifically, although compound-specific isotope analysis of amino acids (CSIA-AA) is becoming a widely used tool, there is little information on how preservation techniques affect amino acid δ15 N values. METHODS: We evaluated the effects of chemical preservatives on bulk tissue δ13 C and δ15 N and amino acid δ15 N values, measured by gas chromatography/isotope ratio mass spectrometry (GC/IRMS), of (a) tuna (Thunnus albacares) and squid (Dosidicus gigas) muscle tissues that were fixed in formaldehyde and stored in ethanol for 2 years and (b) two copepod species, Calanus pacificus and Eucalanus californicus, which were preserved in formaldehyde for 24-25 years. RESULTS: Tissues in formaldehyde-ethanol had higher bulk δ15 N values (+1.4, D. gigas; +1.6‰, T. albacares), higher δ13 C values for D. gigas (+0.5‰), and lower δ13 C values for T. albacares (-0.8‰) than frozen samples. The bulk δ15 N values from copepods were not different those from frozen samples, although the δ13 C values from both species were lower (-1.0‰ for E. californicus and -2.2‰ for C. pacificus) than those from frozen samples. The mean amino acid δ15 N values from chemically preserved tissues were largely within 1‰ of those of frozen tissues, but the phenylalanine δ15 N values were altered to a larger extent (range: 0.5-4.5‰). CONCLUSIONS: The effects of preservation on bulk δ13 C values were variable, where the direction and magnitude of change varied among taxa. The changes in bulk δ15 N values associated with chemical preservation were mostly minimal, suggesting that storage in formaldehyde or ethanol will not affect the interpretation of δ15 N values used in ecological studies. The preservation effects on amino acid δ15 N values were also mostly minimal, mirroring bulk δ15 N trends, which is promising for future CSIA-AA studies of archived specimens. However, there were substantial differences in phenylalanine and valine δ15 N values, which we speculate resulted from interference in the chromatographic resolution of unknown compounds rather than alteration of tissue isotopic composition due to chemical preservation.

Spatial variation in the biochemical and isotopic composition of corals during bleaching and recovery.

Ocean warming and the increased prevalence of coral bleaching events threaten coral reefs. However, the biology of corals during and following bleaching events under field conditions is poorly understood. We examined bleaching and postbleaching recovery in Montipora capitata and Porites compressa corals that either bleached or did not bleach during a 2014 bleaching event at three reef locations in Kane'ohe Bay, O'ahu, Hawai'i. We measured changes in chlorophylls, tissue biomass, and nutritional plasticity using stable isotopes (δ 13C, δ 15N). Coral traits showed significant variation among periods, sites, bleaching conditions, and their interactions. Bleached colonies of both species had lower chlorophyll and total biomass, and while M. capitata chlorophyll and biomass recovered 3 months later, P. compressa chlorophyll recovery was location dependent and total biomass of previously bleached colonies remained low. Biomass energy reserves were not affected by bleaching, instead M. capitata proteins and P. compressa biomass energy and lipids declined over time and P. compressa lipids were site specific during bleaching recovery. Stable isotope analyses did not indicate increased heterotrophic nutrition in bleached colonies of either species, during or after thermal stress. Instead, mass balance calculations revealed that variations in δ 13C values reflect biomass compositional change (i.e., protein : lipid : carbohydrate ratios). Observed δ 15N values reflected spatiotemporal variability in nitrogen sources in both species and bleaching effects on symbiont nitrogen demand in P. compressa. These results highlight the dynamic responses of corals to natural bleaching and recovery and identify the need to consider the influence of biomass composition in the interpretation of isotopic values in corals.

Differences in the trophic ecology of micronekton driven by diel vertical migration.

Many species of micronekton perform diel vertical migrations (DVMs), which ultimately contributes to carbon export to the deep sea. However, not all micronekton species perform DVM, and the nonmigrators, which are often understudied, have different energetic requirements that might be reflected in their trophic ecology. We analyze bulk tissue and whole animal stable nitrogen isotopic compositions (δ 15N values) of micronekton species collected seasonally between 0 and 1250 m depth to explore differences in the trophic ecology of vertically migrating and nonmigrating micronekton in the central North Pacific. Nonmigrating species exhibit depth-related increases in δ 15N values mirroring their main prey, zooplankton. Higher variance in δ 15N values of bathypelagic species points to the increasing reliance of deeper dwelling micronekton on microbially reworked, very small suspended particles. Migrators have higher δ 15N values than nonmigrators inhabiting the epipelagic zone, suggesting the consumption of material during the day at depth, not only at night when they migrate closer to the surface. Migrating species also appear to eat larger prey and exhibit a higher range of variation in δ 15N values seasonally than nonmigrators, likely because of their higher energy needs. The dependence on material at depth enriched in 15N relative to surface particles is higher in migratory fish that ascend only to the lower epipelagic zone. Our results confirm that stark differences in the food habits and dietary sources of micronekton species are driven by vertical migrations.

Assessing seasonal changes in animal diets with stable-isotope analysis of amino acids: a migratory boreal songbird switches diet over its annual cycle.

Tools to study seasonal changes in animal diets are needed to address a wide range of ecological questions. This is especially true of migratory animals that experience distinct environments where diets may be substantially different. However, tracking diets of individuals that move vast distances has proven difficult. Compound-specific isotope analysis has emerged as a valuable tool to study diets but has been little used to study dietary changes of migratory animals. Using this technique, we quantify seasonal variation in the annual diet of a migratory songbird (gray-cheeked thrush, Catharus minimus) and test the hypothesis that migrants change their diet in response to the energetic requirements of different periods of the annual cycle. By measuring δ13C and δ15N values of amino acids from feathers grown on the breeding grounds, blood formed during migration and claw grown on the wintering grounds, we found that migration is associated with greater consumption of fruit, compared to the breeding or wintering periods. This was confirmed by the lower trophic position of blood compared to feather and claw, by a decrease in the δ15N value of the source amino acid phenylalanine in blood as a function of days of stopover, and by the positive correlation between δ15N and δ13C values of phenylalanine in blood, and not in feather or claw. This study illustrates how isotopic analysis of amino acids can contribute to understand food webs, seasonal dietary changes and metabolic routing of nutrients in migratory animals.

Long-term trends in the foraging ecology and habitat use of an endangered species: an isotopic perspective.

Evaluating long-term drivers of foraging ecology and population productivity is crucial for providing ecological baselines and forecasting species responses to future environmental conditions. Here, we examine the trophic ecology and habitat use of North Atlantic leatherback turtles (St. Croix nesting population) and investigate the effects of large-scale oceanographic conditions on leatherback foraging dynamics. We used bulk and compound-specific nitrogen isotope analysis of amino acids (CSIA-AA) to estimate leatherback trophic position (TP) over an 18-year period, compare these estimates with TP estimates from a Pacific leatherback population, and elucidate the pre-nesting habitat use patterns of leatherbacks. Our secondary objective was to use oceanographic indices and nesting information from St. Croix leatherbacks to evaluate relationships between trophic ecology, nesting parameters, and regional environmental conditions measured by the North Atlantic Oscillation (NAO) and Atlantic Multidecadal Oscillation. We found no change in leatherback TP over time and no difference in TP between Atlantic and Pacific leatherbacks, indicating that differences in trophic ecology between populations are an unlikely driver of the population dichotomy between Pacific and Atlantic leatherbacks. Isotope data suggested that St. Croix leatherbacks inhabit multiple oceanic regions prior to nesting, although, like their conspecifics in the Pacific, individuals exhibit fidelity to specific foraging regions. Leatherback nesting parameters were weakly related to the NAO, which may suggest that positive NAO phases benefit St. Croix leatherbacks, potentially through increases in resource availability in their foraging areas. Our data contribute to the understanding of leatherback turtle ecology and potential mechanistic drivers of the dichotomy between populations of this protected species.

Oxidation of urea-derived nitrogen by thaumarchaeota-dominated marine nitrifying communities.

Urea nitrogen has been proposed to contribute significantly to nitrification by marine thaumarchaeotes. These inferences are based on distributions of thaumarchaeote urease genes rather than activity measurements. We found that ammonia oxidation rates were always higher than oxidation rates of urea-derived N in samples from coastal Georgia, USA (means ± SEM: 382 ± 35 versus 73 ± 24 nmol L-1  d-1 , Mann-Whitney U-test p < 0.0001), and the South Atlantic Bight (20 ± 8.8 versus 2.2 ± 1.7 nmol L-1  d-1 , p = 0.026) but not the Gulf of Alaska (8.8 ± 4.0 versus 1.5 ± 0.6, p > 0.05). Urea-derived N was relatively more important in samples from Antarctic continental shelf waters, though the difference was not statistically significant (19.4 ± 4.8 versus 12.0 ± 2.7 nmol L-1  d-1 , p > 0.05). We found only weak correlations between oxidation rates of urea-derived N and the abundance or transcription of putative Thaumarchaeota ureC genes. Dependence on urea-derived N does not appear to be directly related to pH or ammonium concentrations. Competition experiments and release of 15 NH3 suggest that urea is hydrolyzed to ammonia intracellularly, then a portion is lost to the dissolved pool. The contribution of urea-derived N to nitrification appears to be minor in temperate coastal waters, but may represent a significant portion of the nitrification flux in Antarctic coastal waters.

Synthesis of Partially Hydrogenated Cycloparaphenylenes with Bent and Fused Structures Bearing Armchair Carbon Nanotube-like Connections.

The Diels-Alder reactions between 2 equiv of (E,E)-1,4-bis(4-bromophenyl)-1,3-butadiene and 1,4-benzoquinone led to the formation of a key intermediate with all four 4-bromophenyl substituents cis to one another. The subsequent nickel-mediated homocoupling reactions then produced partially hydrogenated cycloparaphenylenes, including a molecule bearing two units of tetrahydro[6]cycloparaphenylene (4H[6]CPP) fused together through two 1,4-dimethoxybenzene units in an armchair (6,6)carbon nanotube-like connection. Similarly, two 6H[9]CPPs were connected through three 1,4-dimethoxybenzene units in an armchair (9,9)carbon nanotube-like arrangement. A bent 8H[12]CPP and a bent 12H[18]CPP, which were fused intramolecularly with two and three 1,4-dimethoxybenzene units, respectively, to create the bent structures, were likewise synthesized. A molecule containing a bent 8H[12]CPP fused to a 4H[6]CPP was likewise constructed. The structures of these partially hydrogenated CPPs were established by X-ray structure analysis, NMR spectroscopy, and additional independent synthetic pathways.

Synthesis and Characterization of Functionalized [12]Cycloparaphenylenes Containing Four Alternating Biphenyl and Naphthyl Units.

Functionalized [12]cycloparaphenylenes ([12]CPPs) containing four alternating biphenyl and naphthyl units were synthesized. A macrocyclic furan-containing CPP precursor was used for the Diels-Alder reaction with the parent benzyne or 3,6-dimethoxybenzyne to form the corresponding macrocyclic carbon frameworks. The subsequent reductive deoxygenation of the Diels-Alder adducts with Fe2(CO)9 followed by oxidative aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone produced the functionalized [12]CPPs. The effect of macrocyclic ring size on the reaction rate of oxidative aromatization was investigated.

Carbon, Nitrogen, and Mercury Isotope Evidence for the Biogeochemical History of Mercury in Hawaiian Marine Bottomfish.

The complex biogeochemical cycle of Hg makes identifying primary sources of fish tissue Hg problematic. To identify sources and provide insight into this cycle, we combined carbon (δ13C), nitrogen amino acid (δ15NPhe), and Hg isotope (Δ199Hg, Δ201Hg, δ202Hg) data for six species of Hawaiian marine bottomfish. Results from these isotopic systems identified individuals within species that likely fed from separate food webs. Terrestrial freshwater inputs to coastal sediments were identified as the primary source of tissue Hg in the jack species, Caranx ignobilis, which inhabit shallow marine ecosystems. Thus, coastal C. ignobilis were a biological vector transporting Hg from freshwater environments into marine ecosystems. Depth profiles of Hg isotopic compositions for bottomfish (excludung C. ignobilis) were similar, but not identical, to profiles for open-ocean pelagic fishes, suggesting that in both settings inorganic Hg, which was ultimately transformed to monomethylmercury (MeHg) and bioaccumulated, was dominantly from a single source. However, differences between pelagic fish and bottomfish profiles were attributable to mass-dependent fractionation in the benthos prior to incorporation into the food web. Results also confirmed that bottomfish relied, at least in part, on a benthic food web and identified the incorporation of deeper water oceanic MeHg sources into deeper water sediments prior to food web uptake and transfer.

Diet of the prehistoric population of Rapa Nui (Easter Island, Chile) shows environmental adaptation and resilience.

OBJECTIVES: The Rapa Nui "ecocide" narrative questions whether the prehistoric population caused an avoidable ecological disaster through rapid deforestation and over-exploitation of natural resources. The objective of this study was to characterize prehistoric human diets to shed light on human adaptability and land use in an island environment with limited resources. MATERIALS AND METHODS: Materials for this study included human, faunal, and botanical remains from the archaeological sites Anakena and Ahu Tepeu on Rapa Nui, dating from c. 1400 AD to the historic period, and modern reference material. We used bulk carbon and nitrogen isotope analyses and amino acid compound specific isotope analyses (AA-CSIA) of collagen isolated from prehistoric human and faunal bone, to assess the use of marine versus terrestrial resources and to investigate the underlying baseline values. Similar isotope analyses of archaeological and modern botanical and marine samples were used to characterize the local environment. RESULTS: Results of carbon and nitrogen AA-CSIA independently show that around half the protein in diets from the humans measured came from marine sources; markedly higher than previous estimates. We also observed higher δ15 N values in human collagen than could be expected from the local environment. DISCUSSION: Our results suggest highly elevated δ15 N values could only have come from consumption of crops grown in substantially manipulated soils. These findings strongly suggest that the prehistoric population adapted and exhibited astute environmental awareness in a harsh environment with nutrient poor soils. Our results also have implications for evaluating marine reservoir corrections of radiocarbon dates.

Synthesis of Cycloparaphenylenes Bearing Furan-2,5-diyl or 2,2'-Bifuran-5,5'-diyl Units in the Macrocyclic Structures.

Synthetic pathways to furan-containing cycloparaphenylenes (CPPs) as molecular nanohoops bearing 10, 12, and 15 aromatic units including furan-2,5-diyl or 2,2'-bifuran-5,5'-diyl units have been developed. The X-ray structures of a partially hydrogenated bifuran-containing CPP precursor and the corresponding fully aromatized bifuran-containing CPP were obtained to allow the determination of their conformational arrangements in the crystal lattice. The optical and electrochemical properties of the furan-containing CPPs were investigated.

Mercury sources and trophic ecology for Hawaiian bottomfish.

In Hawaii, some of the most important commercial and recreational fishes comprise an assemblage of lutjanids and carangids called bottomfish. Despite their importance, we know little about their trophic ecology or where the mercury (Hg) that ultimately resides in their tissue originates. Here we investigated these topics, by analyzing muscle samples for mercury content, nitrogen, carbon, and amino acid specific nitrogen isotope ratios in six species distributed across different depths from the Northwestern Hawaiian Islands (NWHI) and the Main Hawaiian Islands (MHI). Fishes had different sources of nitrogen and carbon, with isotopic values suggesting benthic food sources for shallow nearshore species. High trophic position lutjanids that foraged in deeper water, benthic environments generally had higher Hg levels. Model results also suggested that benthic Hg methylation was an important source of Hg for shallow benthic feeders, while deepwater sources of mercury may be important for those with a diet that derives, at least in part, from the pelagic environment. Further, despite the lack of freshwater sources of Hg in the NWHI, statistical models explaining the variation in tissue Hg in the MHI and NWHI were nearly identical, suggesting freshwater Hg inputs were not a major source of Hg in fish tissue.

Meta-analysis of amino acid stable nitrogen isotope ratios for estimating trophic position in marine organisms.

Estimating trophic structures is a common approach used to retrieve information regarding energy pathways, predation, and competition in complex ecosystems. The application of amino acid (AA) compound-specific nitrogen (N) isotope analysis (CSIA) is a relatively new method used to estimate trophic position (TP) and feeding relationships in diverse organisms. Here, we conducted the first meta-analysis of δ(15)N AA values from measurements of 359 marine species covering four trophic levels, and compared TP estimates from AA-CSIA to literature values derived from food items, gut or stomach content analysis. We tested whether the AA trophic enrichment factor (TEF), or the (15)N enrichment among different individual AAs is constant across trophic levels and whether inclusion of δ(15)N values from multiple AAs improves TP estimation. For the TEF of glutamic acid relative to phenylalanine (Phe) we found an average value of 6.6‰ across all taxa, which is significantly lower than the commonly applied 7.6‰. We found that organism feeding ecology influences TEF values of several trophic AAs relative to Phe, with significantly higher TEF values for herbivores compared to omnivores and carnivores, while TEF values were also significantly lower for animals excreting urea compared to ammonium. Based on the comparison of multiple model structures using the metadata of δ(15)N AA values we show that increasing the number of AAs in principle improves precision in TP estimation. This meta-analysis clarifies the advantages and limitations of using individual δ(15)N AA values as tools in trophic ecology and provides a guideline for the future application of AA-CSIA to food web studies.

Tracing the biosynthetic source of essential amino acids in marine turtles using delta13C fingerprints.

Plants, bacteria, and fungi produce essential amino acids (EAAs) with distinctive patterns of delta13C values that can be used as naturally occurring fingerprints of biosynthetic origin of EAAs in a food web. Because animals cannot synthesize EAAs and must obtain them from food, their tissues reflect delta13C(EAA) patterns found in diet, but it is not known how microbes responsible for hindgut fermentation in some herbivores influence the delta13C values of EAAs in their hosts' tissues. We examined whether distinctive delta13C fingerprints of hindgut flora are evident in the tissues of green turtles (Chelonia mydas), which are known to be facultative hindgut fermenters. We determined delta13C(EAA) values in tissues of green turtles foraging herbivorously in neritic habitats of Hawaii and compared them with those from green, olive ridley, and loggerhead turtles foraging carnivorously in oceanic environments of the central and southeast Pacific Ocean. Results of multivariate statistical analysis revealed two distinct groups that could be distinguished based on unique delta13C(EAA) patterns. A three-end-member predictive linear discriminant model indicated that delta13C(EAA) fingerprints existed in the tissues of carnivorous turtles that resembled patterns found in microalgae, which form the base of an oceanic food web, whereas herbivorous turtles derive EAAs from a bacterial or seagrass source. This study demonstrates the capacity for delta13C fingerprinting to establish the biosynthetic origin of EAAs in higher consumers, and that marine turtles foraging on macroalgal diets appear to receive nutritional supplementation from bacterial symbionts in their digestive system.

Reconstructing transoceanic migration patterns of Pacific bluefin tuna using a chemical tracer toolbox.

Large pelagic predators play important roles in oceanic ecosystems, and may migrate vast distances to utilize resources in different marine ecoregions. Understanding movement patterns of migratory marine animals is critical for effective management, but often challenging, due to the cryptic habitat of pelagic migrators and the difficulty of assessing past movements. Chemical tracers can partially circumvent these challenges by reconstructing recent migration patterns. Pacific bluefin tuna (Thunnus orientalis; PBFT) inhabit the western and eastern Pacific Ocean, and are in steep decline due to overfishing. Understanding age-specific eastward transpacific migration patterns can improve management practices, but these migratory dynamics remain largely unquantified. Here, we combine a Fukushima-derived radiotracer (134Cs) with bulk tissue and amino acid stable isotope analyses of PBFT to distinguish recent migrants from residents of the eastern Pacific Ocean. The proportion of recent migrants to residents decreased in older year classes, though the proportion of older PBFT that recently migrated across the Pacific was greater than previous estimates. This novel toolbox of biogeochemical tracers can be applied to any species that crosses the North Pacific Ocean.

Global declines in oceanic nitrification rates as a consequence of ocean acidification.

Ocean acidification produced by dissolution of anthropogenic carbon dioxide (CO(2)) emissions in seawater has profound consequences for marine ecology and biogeochemistry. The oceans have absorbed one-third of CO(2) emissions over the past two centuries, altering ocean chemistry, reducing seawater pH, and affecting marine animals and phytoplankton in multiple ways. Microbially mediated ocean biogeochemical processes will be pivotal in determining how the earth system responds to global environmental change; however, how they may be altered by ocean acidification is largely unknown. We show here that microbial nitrification rates decreased in every instance when pH was experimentally reduced (by 0.05-0.14) at multiple locations in the Atlantic and Pacific Oceans. Nitrification is a central process in the nitrogen cycle that produces both the greenhouse gas nitrous oxide and oxidized forms of nitrogen used by phytoplankton and other microorganisms in the sea; at the Bermuda Atlantic Time Series and Hawaii Ocean Time-series sites, experimental acidification decreased ammonia oxidation rates by 38% and 36%. Ammonia oxidation rates were also strongly and inversely correlated with pH along a gradient produced in the oligotrophic Sargasso Sea (r(2) = 0.87, P < 0.05). Across all experiments, rates declined by 8-38% in low pH treatments, and the greatest absolute decrease occurred where rates were highest off the California coast. Collectively our results suggest that ocean acidification could reduce nitrification rates by 3-44% within the next few decades, affecting oceanic nitrous oxide production, reducing supplies of oxidized nitrogen in the upper layers of the ocean, and fundamentally altering nitrogen cycling in the sea.