Long-finned pilot whale population diversity and structure in Atlantic waters assessed through biogeochemical and genetic markers

Acknowledgements. Cetacean samples were collected under the auspices of stranding monitoring programs run by the Sociedade Portuguesa de Vida Selvagem, the Coordinadora para o Estudio dos Mamíferos Mariños (supported by the regional government Xunta de Galicia), the UK Cetacean Strandings Investigation Programme and the Scottish Agriculture College Veterinary Science Division (jointly funded by Defra and the Devolved Governments of Scotland and Wales), the Marine Mammals Research Group of the Institute of Marine Research (Norway), the Museum of Natural History of the Faroe Islands and the International Fund for Animal Welfare Marine Mammal Rescue and Research Program (USA). The authors thank all the members of these institutions and organizations for their assistance with data and sample collection. S.S.M., P.M.F. and M.F. were supported by PhD grants from the Fundação para a Ciência e Tecnologia (POPH/FSE ref SFRH/BD/ 38735/ 2007, SFRH/BD/36766/2007 and SFRH/BD/30240/ 2006, respectively). A.L. was supported by a postdoctoral grant from the Fundação para a Ciência e Tecnologia (ref SFRH/BPD/82407/2011). The work related to strandings and tissue collection in Portugal was partially supported by the SafeSea project EEAGrants PT 0039 (supported by Iceland, Liechtenstein and Norway through the EEA Financial Mechanism), the MarPro project Life09 NAT/PT/000038 (funded by the European Union program LIFE+) and the project CetSenti FCT RECI/AAG-GLO/0470/2012 (FCOMP- 01-0124-FEDER-027472) (funded by the program COMPETE and the Fundação para a Ciência e Tecnologia). G.J.P. thanks the University of Aveiro and Caixa Geral de Depósitos (Portugal) for financial support. The authors acknowledge the assistance of the chemical analysts at Marine Scotland Science with the fatty acid analysis.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials

Electrical properties of platinum interconnects deposited by electron beam induced deposition of the carbon-free precursor, Pt(PF3)4

Comprehensive analysis of the electrical properties, structure and composition of Pt interconnects, developed via mask-less, electron beam induced deposition of the carbon-free Pt precursor, Pt(PF3)4, is presented. The results demonstrate significantly improved electrical performance in comparison with that generated from the standard organometallic precursor, (CH3)3Pt(CpCH3). In particular, the Pt interconnects exhibited perfect ohmic behavior and resistivity that can be diminished to 0.24 × 10−3 Ω cm, which is only one order of magnitude higher than bulk Pt, in comparison to 0.2 Ω cm for the standard carbon-containing interconnects. A maximum current density of 1.87 × 107 A cm−2 was achieved for the carbon-free Pt, compared to 9.44 × 105 A cm−2 for the standard Pt precursor. The enhanced electrical properties of the as-deposited materials can be explained by the absence of large amounts of carbon impurities, and their further improvement by postdeposition annealing in N2. In-situ TEM heating experiments confirmed that the annealing step induces sintering of the Pt nanocrystals and improved crystallinity, which contributes to the enhanced electrical performance. Alternative annealing under reducing conditions resulted in improved performance of the standard Pt interconnects, while the carbon-free deposit suffered electrical and structural breakage due to formation of larger Pt islands

Structure, Morphology, and Electrochemical Properties of Transition Metal Oxide, Hydroxide, and Phosphate Nanomaterials for Energy Storage

Energy storage technologies are crucial for efficient utilization of electricity. Supercapacitors and rechargeable batteries are of currently available energy storage systems. Transition metal oxides, hydroxides, and phosphates are the most intensely investigated electrode materials for supercapacitors and rechargeable batteries due to their high theoretical charge storage capacities resulted from reversible electrochemical reactions. Their insulating nature, however, causes sluggish electron transport kinetics within these electrode materials, hindering them from reaching the theoretical maximum. The conductivity of these transition metal based-electrode materials can be improved through three main approaches; nanostructuring, chemical substitution, and introducing carbon matrices. These approaches often lead to unique electrochemical properties when combined and balanced.

Ethanol-mediated solvothermal synthesis we developed is found to be highly effective for controlling size and morphology of transition metal-based electrode materials for both pseudocapacitors and batteries. The morphology and the degree of crystallinity of nickel hydroxide are systematically changed by adding various amounts glucose to the solvothermal synthesis. Nickel hydroxide produced in this manner exhibited increased pseudocapacitance, which is partially attributed to the increased surface area. Interestingly, this morphology effect on cobalt doped-nickel hydroxide is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance.

Moreover, a thin layer of densely packed nickel oxide flakes on carbon paper substrate was successfully prepared via the glucose-assisted solvothermal synthesis, resulting in the improved electrode conductivity. When reduced graphene oxide was used for conductive coating on as-prepared nickel oxide electrode, the electrode conductivity was only slightly improved. This finding reveals that the influence of reduced graphene oxide coating, increasing the electrode conductivity, is not that obvious when the electrode is already highly conductive to begin with.

We were able to successfully control the interlayer spacing and reduce the particle size of layered titanium hydrogeno phosphate material using our ethanol-mediated solvothermal reaction. In layered structure, interlayer spacing is the key parameter for fast ion diffusion kinetics. The nanosized layered structure prepared via our method, however, exhibited high sodium-ion storage capacity regardless of the interlayer spacing, implying that interlayer space may not be the primary factor for sodium-ion diffusion in nanostructured materials, where many interstitials are available for sodium-ion diffusion.

Our ethanol-mediated solvothermal reaction was also effective for synthesis of NaTi2(PO4)3 nanoparticles with uniform size and morphology, well connected by a carbon nanotube network. This composite electrode exhibited high capacity, which is comparable to that in aqueous electrolyte, probably due to the uniform morphology and size where the preferable surface for sodium-ion diffusion is always available in all individual particles.

Fundamental understandings of the relationship between electrode microstructures and electrochemical properties discussed in this dissertation will be important to design high performance energy storage system applications.

Synthesis and characterization of nanocomposites based on PANI and carbon nanostructures prepared by electropolymerization

Nanocomposites based on polyaniline (PANI) and carbon nanostructures (CNSs) (graphene (G) and multiwall carbon nanotubes (MWCNTs)) were prepared by in situ electrochemical polymerization. CNSs were inserted into the PANI matrix by dispersing them into the electrolyte before the electropolymerization. Electrochemical characterization by means of cyclic voltammetry and steady state polarization were performed in order to determine conditions for electro- polymerization. Electro-polymerization of the PANI based nanocomposites was carried out at 0.75 V vs. saturated calomel electrode (SCE) for 40 and 60 minutes. The morphology and structural characteristics of the obtained nanocomposites were studied by scanning electron microscopy (SEM) and Raman spectroscopy, while thermal stability was determined using thermal gravimetric analysis (TGA). According to the morphological and structural study, fibrous and porous structure of PANI based nanocomposites was detected well embedding both G and MWCNTs. Also, strong interaction between quinoidal structure of PANI with carbon nanostructures via π–π stacking was detected by Raman spectroscopy. TGA showed the increased thermal stability of composites reinforced with CNSs, especially those reinforced with graphene.

Chlorine Contribution to Quantitative Structure and Activity Relationship Models of Disinfection By-Products' Quantum Chemical Descriptors and Toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Stable carbon and oxygen isotopes and Mg/Ca ratios of foraminifers from ODP Site 202-1241 sediments

A combination of stable isotope records and Mg/Ca temperature estimates of four different planktonic foraminiferal species from Ocean Drilling Program Site 1241 allows differentiation between temperature and salinity changes in the tropical east Pacific (TEP) upper water column during the Pliocene (~5.7-2.1 Ma). The deviation of d18O records and Mg/Ca temperature estimates from thermocline-dwelling planktonic foraminifers suggests that local changes in salinity exerted a much stronger control on Pliocene TEP upper ocean water mass signatures than previously assumed. The most pronounced Pliocene change in TEP upper ocean stratification was the shoaling of the thermocline from ~4.8 to 4.0 Ma that was possibly triggered by changes in the configuration of low-latitude ocean gateways. During this time interval, mixed-layer temperatures and salinities remained relatively constant in contrast to a pronounced temperature (~6°C) and salinity decrease at the bottom of the photic zone. This change led to a new state in the thermal structure of the TEP, as the thermocline remained relatively shallow until ~2.1 Ma.

(Table 2) Copepod carbon production in the upper 50 m in Godthabsfjord and Fyllas Banke, West Greenland

This study describes differences in plankton community structure and in chemical and physical gradients between the offshore West Greenland Current system and inland regions close to the Greenland Ice Sheet during the post-bloom in Godthabsfjorden (64° N, 51° W). The offshore region had pronounced vertical mixing, with centric diatoms and Phaeocystis spp. dominating the phytoplankton, chlorophyll (chl) a (0.3 to 3.9 µg/l) was evenly distributed and nutrients were depleted in the upper 50 m. Ciliates and heterotrophic dinoflagellates constituted equal parts of the protozooplankton biomass. Copepod biomass was dominated by Calanus spp. Primary production, copepod production and the vertical flux were high offshore. The water column was stratified in the fjord, causing chl a to be concentrated in a thin sub-surface layer. Nutrients were depleted above the pycnocline, and Thalassiosira spp. dominated the phytoplankton assemblage close to the ice sheet. Dinoflagellates dominated the protozooplankton biomass, whereas copepod biomass was low and was dominated by Pseudocalanus spp. and Metridia longa. Primary production was low in the outer part of the fjord but considerably higher in the inner parts of the fjord. Copepod production was exceeded by protozooplankton production in the fjord. The results of both physical/chemical factors and biological parameters suggest separation of offshore and fjord systems.

Chlorophyll-a, primary production rates, carbon concentrations and cell counts of coccolithophores, diatoms and microzooplankton measured in water samples from the North Atlantic during the M87/1 cruise in April 2012

The Deep Convection cruise repeatedly sampled two locations in the North Atlantic, sited in the Iceland and Norwegian Basins, onboard the RV Meteor (19 March - 2 May 2012). Samples were collected from multiple casts of a conductivity-temperature-depth (CTD) - Niskin rosette at each station. Water samples for primary production rates, community structure, chlorophyll a [Chl a], calcite [PIC], particulate organic carbon [POC] and biogenic silicic acid [BSi] were collected from predawn casts from six light depths (55%, 20%, 14%, 7%, 5% and 1% of incident PAR). Additional samples for community structure and ancillary parameters were collected from a second cast. Carbon fixation rates were determined using the 13C stable isotope method. Water samples for diatom and micro zooplankton counts, collected from the predawn casts, were preserved with acidic Lugol's solution (2% final solution) and counted using an inverted light microscope. Water samples for coccolithophore counts were collected onto cellulose nitrate filters and counted using polarising light microscopy. Water samples for Chl a analysis were filtered onto MF300 and polycarbonate filters and extracted in 90% acetone. PIC and BSi samples were filtered onto polycarbonate filters and analysed using an inductively coupled plasma emission optical spectrometer and a SEAL QuAAtro autoanalyser respectively.

Meiofauna and the structure of the benthic community in the Iberian deep sea basin

1. On the cruises 3 and 15 of R.V. "Meteor" 6 grab samples, and 6 hauls with the 6 m Agassiztrawl were taken and at 2 stations the deep sea camera was lowered. This material gave quantitative results on the meiofauna and minimum counts of the macrofauna. 2. The nematodes constitute nearly 95% of the meiofauna, the copepoda only 2%. With increasing sediment depth the density of animals decrease gradually. In the uppermost centimeter of sediment 42.6% of the meiofauna are found while only 3.7% live in layer 6-7 cm. Meiofauna weight ranges from 0.6-5.7 mg/25 m**2 surface i.e. 0.24-2.8 g/m**2. 3. Mean numbers of individuals and weights show standard errors of 20-30 %. As an approximate average values for further considerations the weight of the meiofauna in the area was taken as 1 g/m**2 4. Quantitative information on the macrofauna is derived from the trawls and the photographs for the actinia Chitonanthus abyssorum only, which is found in the rate of 1 individual/36-72 m**2, but seems to be less abundant generally. 5. Animal density does not decrease steadily from nearshore to offshore biocoenoses, i.e. generally with increasing depth. The decrease is more pronounced for macro- than for meiofauna. For the deep sea the weight proportion of macrofauna : meiofauna is of the order of 1 : 1. 6. With the assumption, that adaptation of metabolism to deep sea conditions is similar in macro- and meiofauna total metabolism of invertebrates is ascribed to meiofauna to more than 80%. 7. The structure of the biocoenosis of the deep sea floor is characterized by the meiofauna living on and in the sediment and by the dominance of sediment feeders in the macrofauna. 8. Considering the large numbets and high partition rates of bacteria a comparative large part of the metabolism in the deep sea sediment must be ascribed to bacteria. This favours the hypothesis, that with increasing depth and decreasing addition of organic material to the sediment, the importance of meiofauna and microorganisms for total metabolism increases. 9. Considering the different modes of food transport to the deep sea environment, i.e. sinking of dead particles, transport by vertical migration of organisms, aggregation of organic particles, adsorption of dissoloved organic substance to inorganic particles, and heterotrophy, the sediment may be assumed to contain more food for invertebrates than the water above the bottom. 10. Suspensions feeders of macrofauna are fixed to hard substrates in the sediment surface. Some of them are shown to bend themselves down to the bottom in underwater photographs. This suggests the idea that some deep sea suspension feeders partly depend on food from the sediment surface, on which they feed directly.

Effect of enhanced pCO2 levels on the production of dissolved organic carbon and transparent exopolymer particles in short-term bioassay experiments

It has been proposed that increasing levels of pCO2 in the surface ocean will lead to more partitioning of the organic carbon fixed by marine primary production into the dissolved rather than the particulate fraction. This process may result in enhanced accumulation of dissolved organic carbon (DOC) in the surface ocean and/or concurrent accumulation of transparent exopolymer particles (TEPs), with important implications for the functioning of the marine carbon cycle. We investigated this in shipboard bioassay experiments that considered the effect of four different pCO2 scenarios (ambient, 550, 750 and 1000 µatm) on unamended natural phytoplankton communities from a range of locations in the northwest European shelf seas. The environmental settings, in terms of nutrient availability, phytoplankton community structure and growth conditions, varied considerably between locations. We did not observe any strong or consistent effect of pCO2 on DOC production. There was a significant but highly variable effect of pCO2 on the production of TEPs. In three of the five experiments, variation of TEP production between pCO2 treatments was caused by the effect of pCO2 on phytoplankton growth rather than a direct effect on TEP production. In one of the five experiments, there was evidence of enhanced TEP production at high pCO2 (twice as much production over the 96 h incubation period in the 750 ?atm treatment compared with the ambient treatment) independent of indirect effects, as hypothesised by previous studies. Our results suggest that the environmental setting of experiments (community structure, nutrient availability and occurrence of phytoplankton growth) is a key factor determining the TEP response to pCO2 perturbations.

Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.

CoO nanoparticles embedded in three-dimensional nitrogen/sulfur co-doped carbon nanofiber networks as a bifunctional catalyst for oxygen reduction/evolution reactions

High-performance and low-cost bifunctional electrocatalysts play crucial roles in oxygen reduction and evolution reactions. Herein, a novel three-dimensional (3D) bifunctional electrocatalyst was prepared by embedding CoO nanoparticles into nitrogen and sulfur co-doped carbon nanofiber networks (denoted as CoO@N/S-CNF) through a facile approach. The carbon nanofiber networks were derived from a nanostructured biological material which provided abundant functional groups to nucleate and anchor nanoparticles while retaining its interconnected 3D porous structure. The composite possesses a high specific surface area and graphitization degree, which favors both mass transport and charge transfer for electrochemical reaction. The CoO@N/S-CNF not only exhibits highly efficient catalytic activity towards oxygen reduction reaction (ORR) in alkaline media with an onset potential of about 0.84 V, but also shows better stability and stronger resistance to methanol than Pt/C. Furthermore, it only needs an overpotential of 1.55 V to achieve a current density of 10 mA cm^-2, suggesting that it is an efficient electrocatalyst for oxygen evolution reaction (OER). The ΔE value (oxygen electrode activity parameter) of CoO@N/S-CNF is calculated to be 0.828 V, which demonstrates that the composite could be a promising bifunctional electrocatalyst for both ORR and OER.

Effect of heat treatment on reactivity-strength of alkali-activated natural pozzolans

Natural pozzolans can be activated and condensed with sodium silicate in an alkaline environment to synthesize high performance cementitious construction materials with low environmental impact. The nature of the starting materials including mineral composition, chemical composition and crystal structure groups affects the formation of the geopolymer gel phase. In this paper, the pozzolanic activities of five natural pozzolans are studied. From XRD and XRF results, most of the raw materials contain zeolite clay minerals and have a high loss on ignition. Therefore, before use, samples were calcined at 700, 800 and 900 °C, respectively. The improvement in pozzolanic properties was studied following heat treatment including calcinations and/or elevated curing temperature by using alkali solubility and compressive strength tests. The results show that pozzolan containing sodium zeolite clinoptilolite can be used to prepare a moderate to high strength binder by heat treatment and calcinations can impart disorder hornblende as a constituent of pozzolan with no amorphous phase to prepare a moderate strength binder.