Potential biases in dietary interpretation derived from stable isotope analysis of small dolphin teeth.

We analyzed δ13C and δ15N values in different tooth portions (Growth Layer Groups, GLGs) of franciscanas, Pontoporia blainvillei, to investigate their effect on whole tooth (WT) isotopic values and the implications for dietary estimates. Tooth portions included the dentin deposited during the prenatal development (PND), the first year of life (GLG1) deposited during the nursing period and the central part of the tooth with no distinction amongst subsequent GLGs (Center). Isotopic mixing models estimating the contribution of PND, GLG1 and Center to WT showed that GLG1 has a strong effect on WT isotope values in juveniles, while Center only starts to affect WT isotopic values from age four. Isotopic mixing models estimating prey contribution to the diet of juveniles using WT vs Center tooth portions significantly differed in dietary outputs, demonstrating that GLG1 influence on WT isotope values affects dietary estimates in young franciscanas. As the small tooth size and narrowness of the last GLGs hinder the analysis of individual layers, we recommend excluding GLG1 in studies based on teeth isotope composition in franciscanas and caution when interpreting isotopic values from the WT of other small cetaceans.

Strong Margin Influence on the Arctic Ocean Barium Cycle Revealed by Pan-Arctic Synthesis.

Early studies revealed relationships between barium (Ba), particulate organic carbon and silicate, suggesting applications for Ba as a paleoproductivity tracer and as a tracer of modern ocean circulation. But, what controls the distribution of barium (Ba) in the oceans? Here, we investigated the Arctic Ocean Ba cycle through a one-of-a-kind data set containing dissolved (dBa), particulate (pBa), and stable isotope Ba ratio (δ138Ba) data from four Arctic GEOTRACES expeditions conducted in 2015. We hypothesized that margins would be a substantial source of Ba to the Arctic Ocean water column. The dBa, pBa, and δ138Ba distributions all suggest significant modification of inflowing Pacific seawater over the shelves, and the dBa mass balance implies that ∼50% of the dBa inventory (upper 500 m of the Arctic water column) was supplied by nonconservative inputs. Calculated areal dBa fluxes are up to 10 µmol m-2 day-1 on the margin, which is comparable to fluxes described in other regions. Applying this approach to dBa data from the 1994 Arctic Ocean Survey yields similar results. The Canadian Arctic Archipelago did not appear to have a similar margin source; rather, the dBa distribution in this section is consistent with mixing of Arctic Ocean-derived waters and Baffin Bay-derived waters. Although we lack enough information to identify the specifics of the shelf sediment Ba source, we suspect that a sedimentary remineralization and terrigenous sources (e.g., submarine groundwater discharge or fluvial particles) are contributors.

Combining isotopic analysis of bulk-skin and individual amino acids to investigate the trophic position and foraging areas of multiple cetacean species in the western South Atlantic.

We investigated the trophic structure and habitat use of ten cetacean species occurring in the oceanic waters of the western South Atlantic using naturally-occurring stable isotopes. We analysed δ15N in individual amino acids (AA) to estimate cetacean trophic position (TP) and to evaluate the spatial differences in baseline δ15N (source AAs). We adjusted cetacean bulk-skin δ13C and δ15N for the effect of trophic level using their estimated TPs, obtaining δ13CAdjusted and δ15NAdjusted, respectively. These values were applied to estimate the overlap in the niche areas of cetacean baseline sources. Our analyses showed spatial segregation between Steno bredanensis and the remaining odontocetes, and the high δ15N in this species reflects its occurrence in neritic waters of the southern region. The highest TPs were observed in Physeter macrocephalus, Stenella attenuata and Globicephala melas, while the lowest TPs were reported for S. longirostris, S. clymene and Orcinus orca. Overall, source AA-δ15N showed similar patterns as those of baseline-δ15N (zooplankton) and were higher in species sampled in the southernmost region of the study area (e.g., Delphinus delphis). Isotopic niche areas estimated using δ13CAdjusted and δ15NAdjusted suggested high overlap in foraging area between S. frontalis and Tursiops truncatus, with the latter occupying a higher TP. Our analyses of δ15N in AAs provide a unique insight into the trophic ecology, forage areas and spatial segregation in resource use among these cetacean populations. Additionally, our work provides AA-δ15N baseline for future studies on the trophic ecology and habitat use of marine organisms in the western South Atlantic.

Revisiting the distribution of oceanic N2 fixation and estimating diazotrophic contribution to marine production.

Marine N2 fixation supports a significant portion of oceanic primary production by making N2 bioavailable to planktonic communities, in the process influencing atmosphere-ocean carbon fluxes and our global climate. However, the geographical distribution and controlling factors of marine N2 fixation remain elusive largely due to sparse observations. Here we present unprecedented high-resolution underway N2 fixation estimates across over 6000 kilometers of the western North Atlantic. Unexpectedly, we find increasing N2 fixation rates from the oligotrophic Sargasso Sea to North America coastal waters, driven primarily by cyanobacterial diazotrophs. N2 fixation is best correlated to phosphorus availability and chlorophyll-a concentration. Globally, intense N2 fixation activity in the coastal oceans is validated by a meta-analysis of published observations and we estimate the annual coastal N2 fixation flux to be 16.7 Tg N. This study broadens the biogeography of N2 fixation, highlights the interplay of regulating factors, and reveals thriving diazotrophic communities in coastal waters with potential significance to the global nitrogen and carbon cycles.

Biological responses of the marine diatom Chaetoceros socialis to changing environmental conditions: A laboratory experiment.

Diatoms constitute a major group of phytoplankton, accounting for ~20% of the world's primary production. It has been shown that iron (Fe) can be the limiting factor for phytoplankton growth, in particular, in the HNLC (High Nutrient Low Chlorophyll) regions. Iron plays thus an essential role in governing the marine primary productivity and the efficiency of biological carbon pump. Oceanic systems are undergoing continuous modifications at varying rates and magnitudes as a result of changing climate. The objective of our research is to evaluate how changing environmental conditions (dust deposition, ocean warming and acidification) can affect marine Fe biogeochemistry and diatom growth. Laboratory culture experiments using a marine diatom Chaetoceros socialis were conducted at two temperatures (13°C and 18°C) and under two pCO2 (carbon dioxide partial pressure) (400 µatm and 800 µatm) conditions. The present study clearly highlights the effect of ocean acidification on enhancing the release of Fe upon dust deposition. Our results also confirm that being a potential source of Fe, dust provides in addition a readily utilizable source of macronutrients such as dissolved phosphate (PO4) and silicate (DSi). However, elevated atmospheric CO2 concentrations may also have an adverse impact on diatom growth, causing a decrease in cell size and possible further changes in phytoplankton composition. Meanwhile, ocean warming may lead to the reduction of diatom production and cell size, inducing poleward shifts in the biogeographic distribution of diatoms. The changing climate has thus a significant implication for ocean phytoplankton growth, cell size and primary productivity, phytoplankton distribution and community composition, and carbon (C), nitrogen (N), phosphorus (P), silicon (Si) and Fe biogeochemical cycles in various ways.

Importance of N2-Fixation on the Productivity at the North-Western Azores Current/Front System, and the Abundance of Diazotrophic Unicellular Cyanobacteria.

To understand the impact of the northwestern Azores Current Front (NW-AzC/AzF) system on HCO3--and N2-fixation activities and unicellular diazotrophic cyanobacteria (UCYN) distribution, we combined geochemical and biological approaches from the oligotrophic surface to upper mesopelagic waters. N2-fixation was observed to sustain 45-85% of the HCO3--fixation in the picoplanktonic fraction performing 47% of the total C-fixation at the deep chlorophyll maximum north and south of the AzF. N2-fixation rates as high as 10.9 µmol N m-3 d-1 and surface nitrate δ15N as low as 2.7‰ were found in the warm (18-24°C), most saline (36.5-37.0) and least productive waters south of the AzF, where UCYN were the least abundant. However, picoplanktonic UCYN abundances up to 55 cells mL-1 were found at 45-200m depths in the coolest nutrient-rich waters north of the AzF. In this area, N2-fixation rates up to 4.5 µmol N m-3 d-1 were detected, associated with depth-integrated H13CO3--fixation rates at least 50% higher than observed south of the AzF. The numerous eddies generated at the NW-AzC/AzF seem to enhance exchanges of plankton between water masses, as well as vertical and horizontal diapycnal diffusion of nutrients, whose increase probably enhances the growth of diazotrophs and the productivity of C-fixers.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES.

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

n-Alkanes and stable C, N isotopic compositions as identifiers of organic matter sources in Posidonia oceanica meadows of Alexandroupolis Gulf, NE Greece.

We analyzed n-alkane contents and their stable carbon isotope composition, as well as the carbon and nitrogen isotope composition (δ(13)C, δ(15)N) of sediment organic matter and different tissues of Posidonia oceanica seagrass sampled in Alexandroupolis Gulf (A.G.), north-eastern Greece, during 2007-2011. n-Alkane contents in P. oceanica and in sediments showed similar temporal trends, but relative to bulk organic carbon content, n-alkanes were much more enriched in sediments compared to seagrass tissue. Individual n-alkanes in sediments had similar values than seagrass roots and rhizomes and were more depleted in (13)C compared to seagrass leaves and sheaths, with δ(13)C values ranging from -35‰ to -28‰ and from -25‰ to -20‰, respectively. n-Alkane indexes such as the Carbon Preference Index, carbon number maximum, and n-alkane proxy 1 (C23+C25/C23+C25+C29+C31) indicate strong inputs of terrestrial organic matter, while the presence of unresolved complex mixtures suggests potential oil pollution in some sampled areas.

Could the acid-base status of Antarctic sea urchins indicate a better-than-expected resilience to near-future ocean acidification?

Increasing atmospheric carbon dioxide concentration alters the chemistry of the oceans towards more acidic conditions. Polar oceans are particularly affected due to their low temperature, low carbonate content and mixing patterns, for instance upwellings. Calcifying organisms are expected to be highly impacted by the decrease in the oceans' pH and carbonate ions concentration. In particular, sea urchins, members of the phylum Echinodermata, are hypothesized to be at risk due to their high-magnesium calcite skeleton. However, tolerance to ocean acidification in metazoans is first linked to acid-base regulation capacities of the extracellular fluids. No information on this is available to date for Antarctic echinoderms and inference from temperate and tropical studies needs support. In this study, we investigated the acid-base status of 9 species of sea urchins (3 cidaroids, 2 regular euechinoids and 4 irregular echinoids). It appears that Antarctic regular euechinoids seem equipped with similar acid-base regulation systems as tropical and temperate regular euechinoids but could rely on more passive ion transfer systems, minimizing energy requirements. Cidaroids have an acid-base status similar to that of tropical cidaroids. Therefore Antarctic cidaroids will most probably not be affected by decreasing seawater pH, the pH drop linked to ocean acidification being negligible in comparison of the naturally low pH of the coelomic fluid. Irregular echinoids might not suffer from reduced seawater pH if acidosis of the coelomic fluid pH does not occur but more data on their acid-base regulation are needed. Combining these results with the resilience of Antarctic sea urchin larvae strongly suggests that these organisms might not be the expected victims of ocean acidification. However, data on the impact of other global stressors such as temperature and of the combination of the different stressors needs to be acquired to assess the sensitivity of these organisms to global change.

Monitoring polycyclic aromatic hydrocarbons in the Northeast Aegean Sea using Posidonia oceanica seagrass and synthetic passive samplers.

The concentrations of 22 polyaromatic hydrocarbons (PAH) in Posidonia oceanica seagrass, sediments, and seawater from the Alexandroupolis Gulf in the Aegean Sea, were investigated from 2007 to 2011. Temporal trends of total PAH contents in P. oceanica and sediments were similar. PAH levels in seawater, sediments, and seagrasses generally decreased with increasing distance from Alexandroupolis Port. Leaves and sheaths of P. oceanica had higher PAH levels than roots and rhizomes. P. oceanica accumulates PAHs and has good potential as a bioindicator of spatiotemporal pollution trends. PAH concentrations were also examined using in situ passive seawater sampling and were compared to results of passive sampling in the laboratory using local sediments and seawater. Levels of high molecular weight PAHs assessed using passive samplers confirmed the decreasing gradient of pollution away from Alexandroupolis Port. Passive sampling also proved useful for investigating sources of PAHs in P. oceanica meadows.

Acid-base physiology response to ocean acidification of two ecologically and economically important holothuroids from contrasting habitats, Holothuria scabra and Holothuria parva.

Sea cucumbers are dominant invertebrates in several ecosystems such as coral reefs, seagrass meadows and mangroves. As bioturbators, they have an important ecological role in making available calcium carbonate and nutrients to the rest of the community. However, due to their commercial value, they face overexploitation in the natural environment. On top of that, occurring ocean acidification could impact these organisms, considered sensitive as echinoderms are osmoconformers, high-magnesium calcite producers and have a low metabolism. As a first investigation of the impact of ocean acidification on sea cucumbers, we tested the impact of short-term (6 to 12 days) exposure to ocean acidification (seawater pH 7.7 and 7.4) on two sea cucumbers collected in SW Madagascar, Holothuria scabra, a high commercial value species living in the seagrass meadows, and H. parva, inhabiting the mangroves. The former lives in a habitat with moderate fluctuations of seawater chemistry (driven by day-night differences) while the second lives in a highly variable intertidal environment. In both species, pH of the coelomic fluid was significantly negatively affected by reduced seawater pH, with a pronounced extracellular acidosis in individuals maintained at pH 7.7 and 7.4. This acidosis was due to an increased dissolved inorganic carbon content and pCO2 of the coelomic fluid, indicating a limited diffusion of the CO2 towards the external medium. However, respiration and ammonium excretion rates were not affected. No evidence of accumulation of bicarbonate was observed to buffer the coelomic fluid pH. If this acidosis stays uncompensated for when facing long-term exposure, other processes could be affected in both species, eventually leading to impacts on their ecological role.

Euechinoidea and Cidaroidea respond differently to ocean acidification.

The impact of the chemical changes in the ocean waters due to the increasing atmospheric CO2 depends on the ability of an organism to control extracellular pH. Among sea urchins, this seems specific to the Euechinoidea, sea urchins except Cidaroidea. However, Cidaroidea survived two ocean acidification periods: the Permian-Trias and the Cretaceous-Tertiary crises. We investigated the response of these two sea urchin groups to reduced seawater pH with the tropical cidaroid Eucidaris tribuloides, the sympatric euechinoid Tripneustes ventricosus and the temperate euechinoid Paracentrotus lividus. Both euechinoid showed a compensation of the coelomic fluid pH due to increased buffer capacity. This was linked to an increased concentration of DIC in the coelomic fluid and thus of bicarbonate ions (most probably originating from the surrounding seawater as isotopic signature of the carbon - δ¹³C - was similar). On the other hand, the cidaroid showed no changes within the coelomic fluid. Moreover, the δ¹³C of the coelomic fluid did not match that of the seawater and was not significantly different between the urchins from the different treatments. Feeding rate was not affected in any species. While euechinoids are able to regulate their extracellular acid-base balance, many questions are still unanswered on the costs of this capacity. On the contrary, cidaroids do not seem affected by a reduced seawater pH. Further investigations need to be undertaken to cover more species and physiological and metabolic parameters in order to determine if energy trade-offs occur and how this mechanism of compensation is distributed among sea urchins.

On climate reconstruction using bivalves: three methods to interpret the chemical signature of a shell.

To improve our understanding of the climate process and to assess the human impact on current global warming, past climate reconstruction is essential. The chemical composition of a bivalve shell is strongly coupled to environmental variations and therefore ancient shells are potential climate archives. The nonlinear nature of the relation between environmental condition (e.g. the seawater temperature) and proxy composition makes it hard to predict the former from the latter, however. In this paper we compare the ability of three nonlinear system identification methods to reconstruct the ambient temperature from the chemical composition of a shell. The comparison shows that nonlinear multi-proxy approaches are potentially useful tools for climate reconstructions and that manifold based methods result in smoother and more precise temperature reconstruction.

Variation in physiological indicators in Bathymodiolus azoricus (Bivalvia: Mytilidae) at the Menez Gwen Mid-Atlantic Ridge deep-sea hydrothermal vent site within a year.

Bathymodiolus azoricus, thriving at Mid-Atlantic Ridge deep vents, benefits from a symbiosis with methane- and sulphide-oxidising (MOX and SOX) bacteria, and feeds on particulate and dissolved organic matter. To investigate the temporal evolution in their nutrition adult mussels were collected from one location at the Menez Gwen vent site (817 m depth) on four occasions between 2006 and 2007 and studied using different techniques, including stable isotope analyses and FISH. Gill and mantle tissues delta13C and delta15N signatures varied by 2-3 per thousand during the year and these variations were linked to fluctuations in tissue condition index, C and N contents and SOX/MOX volume ratios as quantified by 3D-FISH. October and January mussels presented a particularly poor condition, possibly related with the prolonged summer period of low sea-surface primary production and/or with the stress of the transplant to acoustically retrievable cages for the October mussels, and with their reproductive state in January mussels, since they were spawning. Our results point to the possibility that May mussels benefited from a pulse of sinking sea-surface plankton material. Results underline the dependency of stable isotopic signatures on the physiological state of the mussel at the time of collection, and on the type of tissue analyzed.

Revisiting carbon flux through the ocean's twilight zone.

The oceanic biological pump drives sequestration of carbon dioxide in the deep sea via sinking particles. Rapid biological consumption and remineralization of carbon in the "twilight zone" (depths between the euphotic zone and 1000 meters) reduce the efficiency of sequestration. By using neutrally buoyant sediment traps to sample this chronically understudied realm, we measured a transfer efficiency of sinking particulate organic carbon between 150 and 500 meters of 20 and 50% at two contrasting sites. This large variability in transfer efficiency is poorly represented in biogeochemical models. If applied globally, this is equivalent to a difference in carbon sequestration of more than 3 petagrams of carbon per year.

Inter- and intra-annual variations of Pb/Ca ratios in clam shells (Mercenaria mercenaria): a record of anthropogenic lead pollution?

In this study, we re-assess the use of bivalve shells as a proxy of lead pollution. Previous studies have stressed that shells display little variability compared to soft tissues and thus are better for pollution biomonitoring. However, in this manuscript we illustrate that there is large inter- and intra-annual Pb variability between shells of the clam Mercenaria mercenaria collected in North Carolina, USA. Therefore, year to year, as well as intra-annual variations in Pb/Ca ratios should be interpreted with caution. Despite this variability, we were able to obtain an annual Pb chronology from 1949 to 2002 using 11 shells collected at different times which clearly exhibited the late 1970's peak in Pb from leaded gasoline use. This indicates that when enough specimens are pooled together, bivalve shells can be used to reconstruct large, long term changes in environmental Pb concentrations. Our data compare well with other studies of aragonite clams from sites with low regional lead pollution. From this we conclude that the Cape Lookout region of North Carolina has not received extensive pollution over the 1949-2002 period. The Pb concentration in shells growing in the 1949-1976 period was not significantly different from those growing in the 1982-2002 period, although other proxies suggest that the 1949-1976 period should be considerably higher. Therefore, our data suggest that there is still a modern low-level source of Pb in the coastal North Carolina environment.

The fate of organic matter in a papyrus (Cyperus papyrus L.) dominated tropical wetland ecosystem in Nyanza Gulf (Lake Victoria, Kenya) inferred from delta13C and delta15N analysis.

Papyrus swamps usually form at the interface between river inlet and open lake. From one such wetland ecosystem (the Kibos system located in the Nyanza Gulf, Lake Victoria, Kenya), three sediment cores were recovered using piston corer in order to determine the fate of organic matter derived from papyrus and possible nutrient pathways in this system. The coring represented a transect from the river through the floating papyrus mat to the lake. Two short cores were retrieved from the lake and river. One long core (2 m) was recovered on a floating papyrus mat. The C:N ratio showed similar trends down core from the three locations. This may possibly be due to diagenic processes such as autolysis, dissolution and microbial mineralisation occurring in the sediments. Statistical analysis through one-way ANOVA revealed no significant differences in the C:N ratios between stations. Results of the stable carbon isotope ratios revealed that the delta(13)C of the river and lake samples were persistently more negative than -20 per thousand over the whole profile indicating possible contribution from terrestrial derived carbon. Regarding the floating mat core, the delta(13)C values ranged from -18.99 per thousand on the top of the floating mat but gradually increased to -16.82 per thousand towards the bottom of the core indicating possible contribution of carbon from Cyperus papyrus that has a delta(13)C value of -13.45+/-0.62 per thousand. Statistical analysis through one-way ANOVA revealed significant differences in the delta(13)C values between stations. The stable nitrogen isotope values were highly positive both in the river and in the lake station (delta(15)N > 10 per thousand), indicating possible contamination from sewage wastes. Values in the swamp were less positive suggesting first, the formation of ammonium depleted in (15)N from intense organic matter mineralisation, secondly indicating the delta(15)N signal of papyrus and, finally that nitrogen fixation processes were possibly occurring in the swamp. Statistical analysis through one-way ANOVA revealed significant differences in the delta(15)N values between stations. The stable isotope findings suggested that carbon derived from papyrus is retained in the swamp. Impoverished oxygen concentration in the swamp suggests high mineralisation of organic matter in the swamp indicating that the retained papyrus-derived carbon is largely respired. We conclude that further studies should be undertaken to determine the respiration rates in the wetland.

Variability in the origin of carbon substrates for bacterial communities in mangrove sediments.

Organic carbon in mangrove sediments originates from both local sources (mangroves, microphytobenthos) and tidal inputs (e.g. phytoplankton, seagrass-derived material). The relative inputs of these sources may vary strongly, both within and between different mangrove sites. We combined elemental (TOC/TN) and bulk delta13C analysis on sediment cores from various mangrove sites with delta13C data of bacteria-specific phospholipid fatty acids (PLFA) in order to identify the dominant carbon substrates used by in situ bacterial communities. delta13C values of each of these markers showed a range of 10% or more across the different sites and sampling depths, but generally followed the delta13C trend observed in bulk organic carbon. Several sediment cores show a strong vertical gradient in PLFA delta13C, suggesting a selectivity for algal-derived carbon in the surface layers. Our data demonstrate that the origin of bacterial carbon substrates varies widely across different mangrove sites, and imply that data on mineralization of organic matter cannot be directly incorporated in ecosystem carbon budgets without an estimation of the contribution of various sources.