ALBERT

Description: The female flowers (“cones”) of the hop plant (Humulus L.) produce compounds that contribute to the flavor and other properties of beer. Hop leaves and cones produce many of the same compounds, which also confer agronomic traits such as insect and disease resistance. Targeted and untargeted ultraperformance liquid chromatography-quadrupole time-of-flight–mass spectrometry with Waters MSE technology (UPLC-QTof-MSE) metabolomics were used to compare leaf phytochemical compositions of greenhouse-grown southwestern American wild Humulus neomexicanus (A. Nelson and Cockerell) Rydb. against a group of commercial hop cultivars consisting of both pure European Humulus lupulus L. and European–North American hybrids. Principal component analysis showed a clear distinction in chemical profiles between the two groups. H. neomexicanus leaves had a significantly higher content of total α acids (p = 4.4 × 10–9), total bitter acids (p = 2.6 × 10–6), cohumulone (p = 1.0 × 10–13), humulone + adhumulone (p = 9.1 × 10–4), and the prenylflavonoids xanthohumol (p = 0.013) and desmethylxanthohumol (p = 0.029) as well as significantly higher densities of glandular trichomes (p = 1.3 × 10–6), the biosynthetic site of those compounds. Most flavonol glycosides measured were also significantly more abundant in H. neomexicanus (p = 1.5 × 10–22 to 0.0027), whereas phenolic acids were consistently, but generally nonsignificantly (p 〉 0.05), more abundant in the cultivars. The higher bitter acid, prenylflavonoid, and flavonol glycoside content of H. neomexicanus leaves may help to confer more favorable insect and disease-resistance properties.

Description: Iron is an indispensable metabolic cofactor in both pro- and eukaryotes, which engenders a natural competition for the metal between bacterial pathogens and their human or animal hosts. Bacteria secrete siderophores that extract Fe3+ from tissues, fluids, cells, and proteins; the ligand gated porins of the Gram-negative bacterial outer membrane actively acquire the resulting ferric siderophores, as well as other iron-containing molecules like heme. Conversely, eukaryotic hosts combat bacterial iron scavenging by sequestering Fe3+ in binding proteins and ferritin. The variety of iron uptake systems in Gram-negative bacterial pathogens illustrates a range of chemical and biochemical mechanisms that facilitate microbial pathogenesis. This document attempts to summarize and understand these processes, to guide discovery of immunological or chemical interventions that may thwart infectious disease.

Description: While thousands of environmental metagenomes have been mined for the presence of novel biosynthetic gene clusters, such computational predictions do not provide evidence of their in vivo biosynthetic functionality. Using fluorescent in situ enzyme assay targeting carrier proteins common to polyketide (PKS) and nonribosomal peptide synthetases (NRPS), we applied fluorescence-activated cell sorting to tunicate microbiome to enrich for microbes with active secondary metabolic capabilities. Single-cell genomics uncovered the genetic basis for a wide biosynthetic diversity in the enzyme-active cells and revealed a member of marine Oceanospirillales harboring a novel NRPS gene cluster with high similarity to phylogenetically distant marine and terrestrial bacteria. Interestingly, this synthase belongs to a larger class of siderophore biosynthetic gene clusters commonly associated with pestilence and disease. This demonstrates activity-guided single-cell genomics as a tool to guide novel biosynthetic discovery.

Description: Cold‐water coral (CWC) reefs and mounds are and have been biodiversity hotspots of the deep sea. As their occurrence depends on specific environmental parameters, gaining hindsight on changing ocean conditions under on‐going climate change is the key to a better understanding of CWC mound development through time. A convenient technique for reconstructing the palaeoenvironment during periods of CWC mound growth is by extracting geochemical proxies from biologically mediated carbonates. Here, the focus is on probably the two most abundant calcareous archives, that are, cold‐water Scleractinia and Foraminifera, with an overview of the geochemical proxies (selection) used in these aragonitic and calcitic skeletons from CWC mounds. A particular emphasis is set on constraining proxies for temperature, salinity, seawater density, seawater carbonate systems parameters (pH, CO 3 2− ), nutrients, oxygen and water mass tracers.

Description: Marine macroalgae, seaweeds, are exceptionally prolific producers of halogenated natural products. Biosynthesis of halogenated molecules in seaweeds is inextricably linked to reactive oxygen species (ROS) signaling as hydrogen peroxide serves as a substrate for haloperoxidase enzymes that participate in the construction these halogenated molecules. Here, using red macroalga Asparagopsis taxiformis, a prolific producer of the ozone depleting molecule bromoform, we provide the discovery and biochemical characterization of a ROS-producing NAD(P)H oxidase from seaweeds. This discovery was enabled by our sequencing of Asparagopsis genomes, in which we find the gene encoding the ROS-producing enzyme to be clustered with genes encoding bromoform-producing haloperoxidases. Biochemical reconstitution of haloperoxidase activities establishes that fatty acid biosynthesis can provide viable hydrocarbon substrates for bromoform production. The ROS production haloperoxidase enzymology that we describe here advances seaweed biology and biochemistry by providing the molecular basis for decades worth of physiological observations in ROS and halogenated natural product biosyntheses.

Description: Fusarium oxysporum is a destructive root-infecting plant pathogen that causes significant yield losses in many economically important crop species. Hence, a deeper understanding of pathogen infection strategies is needed. With liquid chromatography-tandem mass spectrometry and gas chromatography-time of flight mass spectrometry platforms, we analyzed the metabolic changes in a time-course experiment with Arabidopsis accessions either resistant (Col-0) or susceptible (Ler-0) to isolates of Fusarium oxysporum forma specialis matthioli infection. We showed a concurrent effect of Fusarium-derived polyols and the mycotoxin beauvericin in the suppression of the immune response of susceptible hosts. A significant increase in oxidized glutathione in the resistant host was probably associated with effective reactive oxygen species-mediated resistance responses. Through a combination of targeted and untargeted metabolomics, we demonstrated the concurrent action of several Arabidopsis defense systems as well as the concurrent action of several virulence systems in the fungal attack of susceptible Arabidopsis.

Description: Precipitation extremes with devastating socioeconomic consequences within the South American Monsoon System (SAMS) are expected to become more frequent in the near future. The complexity in SAMS behavior, however, poses severe challenges for reliable future projections. Thus, robust paleomonsoon records are needed to constrain the high spatiotemporal variability in the response of SAMS rainfall to different climatic drivers. This study uses Ti/Ca ratios from X‐ray fluorescence scanning of a sediment core retrieved off eastern Brazilian to trace precipitation changes over the past 322 Kyr. The results indicate that despite the spatiotemporal complexity of the SAMS, insolation forcing is the primary pacemaker of variations in the monsoonal system. Additional modulation by atmospheric p CO 2 suggests that SAMS intensity over eastern Brazil will be suppressed by rising CO 2 emissions in the future. Lastly, our record reveals an unprecedented strong and persistent wet period during Marine Isotope Stage 6 driven by anomalously strong trade winds.

Description: Three monoterpenoid indole alkaloids (MIAs), tabernabovines A–C (1–3), were isolated from Tabernaemontana bovina. They were elucidated by spectroscopic data and computational calculations. Unlike precursors of MIAs, strictosidine and alstrostine A, alkaloid 1 consists of tryptamine and secologanin in a 2:1 ratio. Alkaloid 2 is a cage compound, and 3 possesses a bridged ring. Tabernabovine A exhibited inhibitory activity against NO production with IC50 44.1 μM compared to l-NMMA with IC50 of 48.6 μM.

Description: Euphorkanlide A (1), a highly modified ingenane diterpenoid with a C24 appendage forming an additional hexahydroisobenzofuran-fused 19-membered macrocyclic bis-lactone ring system was isolated from the roots of Euphorbia kansuensis. Its structure was determined by extensive spectroscopic analysis and quantum-chemical calculations. Compound 1 showed significant cytotoxicities against a panel of cancer cell lines (IC50s 〈 5 μM). Mechanistic study revealed that 1 could induce the generation of ROS, leading to cell cycle arrest and cell apoptosis in drug-resistant cancer cell line HCT-15/5-FU.

Description: The vast amount of plastic waste emitted into the environment and the increasing concern of potential harm to wildlife has made microplastic and nanoplastic pollution a growing environmental concern. Plastic pollution has the potential to cause both physical and chemical harm to wildlife directly or via sorption, concentration, and transfer of other environmental contaminants to the wildlife that ingest plastic. Small particles of plastic pollution, termed microplastics (〉100 nm and 〈5 mm) or nanoplastics (〈100 nm), can form through fragmentation of larger pieces of plastic. These small particles are especially concerning because of their high specific surface area for sorption of contaminants as well as their potential to translocate in the bodies of organisms. These same small particles are challenging to separate and identify in environmental samples because their size makes handling and observation difficult. As a result, our understanding of the environmental prevalence of nanoplastics and microplastics is limited. Generally, the smaller the size of the plastic particle, the more difficult it is to separate from environmental samples. Currently employed passive density and size separation techniques to isolate plastics from environmental samples are not well suited to separate microplastics and nanoplastics. Passive flotation is hindered by the low buoyancy of small particles as well as the difficulty of handling small particles on the surface of flotation media. Here we suggest exploring alternative techniques borrowed from other fields of research to improve separation of the smallest plastic particles. These techniques include adapting active density separation (centrifugation) from cell biology and taking advantage of surface-interaction-based separations from analytical chemistry. Furthermore, plastic pollution is often challenging to quantify in complex matrices such as biological tissues and wastewater. Biological and wastewater samples are important matrices that represent key points in the fate and sources of plastic pollution, respectively. In both kinds of samples, protocols need to be optimized to increase throughput, reduce contamination potential, and avoid destruction of plastics during sample processing. To this end, we recommend adapting digestion protocols to match the expected composition of the nonplastic material as well as taking measures to reduce and account for contamination. Once separated, plastics in an environmental sample should ideally be characterized both visually and chemically. With existing techniques, microplastics and nanoplastics are difficult to characterize or even detect. Their low mass and small size provide limited signal for visual, vibrational spectroscopic, and mass spectrometric analyses. Each of these techniques involves trade-offs in throughput, spatial resolution, and sensitivity. To accurately identify and completely quantify microplastics and nanoplastics in environmental samples, multiple analytical techniques applied in tandem are likely to be required.

Description: Noninvasive diagnostic by imaging combined with a contrast agent (CA) is by now the most used technique to get insight into human bodies. X-ray and magnetic resonance imaging (MRI) are widely used technologies providing complementary results. Nowadays, it seems clear that bimodal CAs could be an emerging approach to increase the patient compliance, accessing different imaging modalities with a single CA injection. Owing to versatile designs, targeting properties, and high payload capacity, nanocarriers are considered as a viable solution to reach this goal. In this study, we investigated efficient superparamagnetic iron oxide nanoparticle (SPION)-loaded iodinated nano-emulsions (NEs) as dual modal injectable CAs for X-ray imaging and MRI. The strength of this new CA lies not only in its dual modal contrasting properties and biocompatibility, but also in the simplicity of the nanoparticulate assembling: iodinated oily core was synthesized by the triiodo-benzene group grafting on vitamin E (41.7% of iodine) via esterification, and SPIONs were produced by thermal decomposition during 2, 4, and 6 h to generate SPIONs with different morphologies and magnetic properties. SPIONs with most anisotropic shape and characterized by the highest r2/r1 ratio once encapsulated into iodinated NE were used for animal experimentation. The in vivo investigation showed an excellent contrast modification because of the presence of the selected NEs, for both imaging techniques explored, that is, MRI and X-ray imaging. This work provides the description and in vivo application of a simple and efficient nanoparticulate system capable of enhancing contrast for both preclinical imaging modalities, MRI, and computed tomography.

Description: UPLC–TOF/MS profiling, followed by the recently reported differential off-line LC–NMR (DOLC–NMR) and quantitative 1H NMR spectroscopy (qHNMR), led to the differential qualitative analysis and accurate quantitation of l-tryptophan-induced metabolome alterations of Penicillium roqueforti, which is typically used in making blue-mold cheese. Among the 24 metabolites identified, two tetrapeptides, namely, d-Phe-l-Val-d-Val-l-Tyr and d-Phe-l-Val-d-Val-l-Phe, as well as cis-bis(methylthio)silvatin, are reported for the first time as metabolites of P. roqueforti. Antimicrobial activity tests showed strong effects of the catabolic l-tryptophan metabolites 3-hydroxyanthranilic acid, anthranilic acid, and 3-indolacetic acid against Saccharomyces cerevisiae, with IC50 values between 15.6 and 24.0 μg/mL, while roquefortine C and cis-bis(methylthio)silvatin inhibited the growth of Gram-negative Escherichia coli and Gram-positive Bacillus subtilis with IC50 values between 30.0 and 62.5 μg/mL.

Description: Microplastics (MPs) in aquatic organisms are raising increasing concerns regarding their potential damage to ecosystems. To date, Raman and Fourier transform infrared spectroscopy techniques have been widely used for detection of MPs in aquatic organisms, which requires complex protocols of tissue digestion and MP separation and are time- and reagentconsuming. This novel approach directly separates, identifies, and characterizes MPs from the hyperspectral image (HSI) of the intestinal tract content in combination with a support vector machine classification model, instead of using the real digestion/separation protocols. The procedures of HSI acquisition ( 1 min) and data analysis (5 min) can be completed within 6 min plus the sample preparation and drying time (30 min) where necessary. This method achieved a promising efficiency (recall 〉98.80%, precision 〉96.22%) for identifying five types of MPs (particles 〉0.2 mm). Moreover, the method was also demonstrated to be effective on field fish from three marine fish species, revealing satisfying detection accuracy (particles 〉0.2 mm) comparable to Raman analysis. The present technique omits the digestion protocol (reagent free), thereby significantly reducing reagent consumption, saving time, and providing a rapid and efficient method for MP analysis.

Description: A new olivine reference material – MongOL Sh11‐2 – for in situ analysis has been prepared from a central portion of a large (20 cm × 20 cm × 10 cm) mantle peridotite xenolith from a ~ 0.5 Ma old basaltic breccia at Shavaryn‐Tsaram, Tariat region, central Mongolia. The xenolith is a fertile mantle lherzolite with minimal signs of alteration. Approximately 10 g of 0.5 to 2 mm gem quality olivine fragments were separated under binocular microscope and analysed by EPMA, LA‐ICP‐MS, SIMS and bulk analytical methods (ID ICP‐MS for Mg and Fe, XRF, ICP‐MS) for major, minor and trace elements at six institutions worldwide. The results show that the olivine fragments are sufficiently homogeneous with respect to major (Mg, Fe, Si) and minor and trace elements. Significant inhomogeneity was revealed only for phosphorus (homogeneity index of 12.4), whereas Li, Na, Al, Sc, Ti and Cr show minor inhomogeneity (homogeneity index of 1–2). The presence of some mineral and fluid‐melt micro‐inclusions may be responsible for the inconsistency in mass fractions obtained by in situ and bulk analytical methods for Al, Cu, Sr, Zr, Ga, Dy and Ho. Here we report reference and information values for twenty‐seven major, minor and trace elements.

Description: Aim: The interdependencies between trophic interactions, environmental factors and anthropogenic forcing determine how species distributions change over time. Large changes in species distributions have occurred as a result of climate change. The objective of this study was to analyse how the spatial distribution of cod and flounder has changed in the Baltic Sea during the past four decades characterized by large hydrological changes. Location: Baltic Sea. Taxon: Cod (Gadus morhua) and flounder (Platichthys flesus). Methods: Catch per unit of effort (CPUE) data for adult and juvenile cod and for adult flounder were modelled using Delta-Generalized additive models including environmental and geographical variables between 1979 and 2016. From the annual CPUE predictions for each species, yearly distribution maps and depth distribution curves were obtained. Mean depth and the depth range were estimated to provide an indication on preferred depth and habitat occupancy. Results: Adult and juvenile cod showed a contraction in their distribution in the southern areas of the Baltic Sea. Flounder, instead, showed an expansion in its distribution with an increase in abundance in the northern areas. The depth distributions showed a progressive shift of the mean depth of occurrence towards shallower waters for adult cod and flounder and towards deeper waters for juvenile cod, as well as a contraction of the species depth ranges, evident mainly from the late 1980s. Main conclusions: Our study illustrates large changes in the spatial distribution of cod and flounder in the Baltic Sea. The changes in depth distribution occurred from the late 1980s are probably due to a combination of expanded areas of hypoxia in deep waters and an increase in predation risk in shallow waters. The net effect of these changes is an increased spatial overlap between life stages and species, which may amplify cod cannibalism and the interaction strength between cod and flounder

Description: Microplastics are ubiquitous across ecosystems, yet the exposure risk to humans is unresolved. Focusing on the American diet, we evaluated the number of microplastic particles in commonly consumed foods in relation to their recommended daily intake. The potential for microplastic inhalation and how the source of drinking water may affect microplastic consumption were also explored. Our analysis used 402 data points from 26 studies, which represents over 3600 processed samples. Evaluating approximately 15% of Americans’ caloric intake, we estimate that annual microplastics consumption ranges from 39000 to 52000 particles depending on age and sex. These estimates increase to 74000 and 121000 when inhalation is considered. Additionally, individuals who meet their recommended water intake through only bottled sources may be ingesting an additional 90000 microplastics annually, compared to 4000 microplastics for those who consume only tap water. These estimates are subject to large amounts of variation; however, given methodological and data limitations, these values are likely underestimates.

Description: Latest knowledge on the reactivity of charged nanoparticulate complexants toward aqueous metal ions is discussed in mechanistic detail. We present a rigorous generic description of electrostatic and chemical contributions to metal ion binding by nanoparticulate complexants, and their dependence on particle size, particle type (i.e., reactive sites distributed within the particle body or confined to the surface), ionic strength of the aqueous medium, and the nature of the metal ion. For the example case of soft environmental particles such as fulvic and humic acids, practical strategies are delineated for determining intraparticulate metal ion speciation, and for evaluating intrinsic chemical binding affinities and heterogeneity. The results are compared with those obtained by popular codes for equilibrium speciation modeling (namely NICA-Donnan and WHAM). Physicochemical analysis of the discrepancies generated by these codes reveals the a priori hypotheses adopted therein and the inappropriateness of some of their key parameters. The significance of the characteristic time scales governing the formation and dissociation rates of metal−nanoparticle complexes in defining the relaxation properties and the complete equilibration of the metal− nanoparticulate complex dispersion is described. The dynamic features of nanoparticulate complexes are also discussed in the context of predictions of the labilities and bioavailabilities of the metal species.

Description: The continental expression of global cooling during the Miocene Climate Transition in Central Asia is poorly documented, as the tectonically active setting complicates the correlation of Neogene regional and global climatic developments. This study presents new geochemical data (CaSO 4 content, carbonate δ 13 C and δ 18 O) from the endorheic alluvial‐lacustrine Aktau succession (Ili Basin, south‐east Kazakhstan) combined with findings from the previously published facies evolution. Time series analysis revealed long‐eccentricity forcing of the paleohydrology throughout the entire succession, split into several facies‐dependent segments. Orbital tuning, constrained by new laser ablation U‐Pb dates and a preexisting magnetostratigraphy, places the succession in a 5.0 Ma long interval in the middle to late Miocene (15.6 to 10.6 Ma). The long‐term water accumulation in the Ili Basin followed the timing of the Miocene Climate Transition, suggesting increased precipitation in the catchment area in response to climate cooling and stronger westerly winds. This was paced by minima of the 2.4 Ma eccentricity cycle, which favored the establishment of a discharge playa (~14.3 Ma) and a perennial lake (12.6 to 11.8 Ma). Furthermore, low obliquity amplitudes (nodes) caused a transient weakening of the westerlies at ~13.7 to 13.5 Ma and at ~12.7 Ma, resulting in negative hydrological budgets and salinization. Flooding of the windward Ili Basin coeval with aridification in the leeward basins suggests that the Tian Shan was a climate boundary already in the middle Miocene. Our results emphasize the impact of climate fluctuations on the westerlies' strength and thus on Central Asian hydrology.

Description: To enable quality control of measurement procedures for determinations of Mg isotope amount ratios, expressed as δ26Mg and δ25Mg values, in Earth-surface studies, the δ26Mg and δ25Mg values of eight reference materials (RMs) were determined by inter-laboratory comparison between five laboratories and considering published data, if available. These matrix RMs, including river water SLRS-5, spring water NIST SRM 1640a, Dead Sea brine DSW-1, dolomites JDo-1 and CRM 512, limestone CRM 513, soil NIST SRM 2709a and vegetation NIST SRM 1515 apple leaves, are representative for a wide range of Earth-surface materials from low-temperature environments. The inter-laboratory variability, 2s (twice the standard deviation), of all eight RMs ranges from 0.05 to 0.17‰ in δ26Mg. Thus, it is suggested that all these materials are suitable for validation of δ26Mg and δ25Mg determinations of Earth-surface geochemical studies.

Description: Populations of fishes provide valuable services for billions of people, but face diverse and interacting threats that jeopardize their sustainability. Human population growth and intensifying resource use for food, water, energy and goods are compromising fish populations through a variety of mechanisms, including overfishing, habitat degradation and declines in water quality. The important challenges raised by these issues have been recognized and have led to considerable advances over past decades in managing and mitigating threats to fishes worldwide. In this review, we identify the major threats faced by fish populations alongside recent advances that are helping to address these issues. There are very significant efforts worldwide directed towards ensuring a sustainable future for the world's fishes and fisheries and those who rely on them. Although considerable challenges remain, by drawing attention to successful mitigation of threats to fish and fisheries we hope to provide the encouragement and direction that will allow these challenges to be overcome in the future.

Description: Mass fractions of Sn and In were determined in sixteen geological reference materials including basaltic/mafic (BCR‐2, BE‐N, BHVO‐1, BHVO‐2, BIR‐1, OKUM, W‐2, WS‐E), ultramafic (DTS‐2b, MUH‐1, PCC‐1, UB‐N) and felsic/sedimentary reference materials (AGV‐2, JA‐1, SdAR‐M2, SdAR‐H1). Extensive digestion and ion exchange separation tests were carried out in order to provide high yields (〉 90% for Sn, 〉 85% for In), low total procedural blanks (~ 1 ng for Sn, 〈 3 pg for In) and low analytical uncertainties for the elements of interest in a variety of silicate sample matrices. Replicate analyses (n = 2–13) of Sn‐In mass fractions give a combined measurement uncertainty of 2u that are generally 〈 3% and in agreement with literature data, where available. We present the first high precision In data for reference materials OKUM (32.1 ± 1.5 ng g−1), DTS‐2b (2.03 ± 0.25 ng g−1), MUH‐1 (6.44 ± 0.30 ng g−1), and PCC‐1 (3.55 ± 0.35 ng g−1) as well as the first Sn data for MUH‐1 (0.057 ± 0.010 μg g−1) and DTS‐2b (0.623 ± 0.018 μg g−1).

Description: Sediment core PS1904 reveals continuous records of planktic and benthic foraminiferal stable isotopes (δ18O/δ13C) from the north-eastern Greenland continental margin. The data show good comparability with other records from the Nordic Seas, allowing the stratigraphic range of PS1904 to be dated to Marine Isotope Stage (MIS) 6. Focusing on MIS 5 reveals light δ18O values during MIS 5a compared to the last interglacial peak (MIS 5e) which indicates that surface and bottom water layers were strongly affected by freshwater during the former event. We present two possible scenarios explaining the origin and routing of the freshwater: (i) drainage of a Eurasian proglacial lake coupled with the collapse of the Kara Sea Ice Sheet at the MIS 5b/a boundary, and (ii) destabilization and melting of the nearby Greenland Ice Sheet. Although both scenarios could have acted simultaneously, sediment records from the Eurasian sector of the Arctic Ocean hint at the proglacial lake system in north-western Siberia as the largest freshwater source. Regardless of the actual source, the freshwater lowered the surface ocean salinity causing water column stratification and sea ice expansion. Increased sea-ice abundance led to a higher albedo and probably contributed to the cooling and global ice sheet growth that occurred subsequently during MIS 4.

Description: Methane recovery from artificial hydrate-bearing sandstones by simulated flue gas swapping was tested using a core flooding experimental setup. Seven groups of experiments were conducted to investigate the effect of hydrate saturation as well as the initial porosity and permeability of sandstones on methane production and carbon dioxide capture. The results show that the CH4 recovery efficiency and the amount of CO2 captured increase with the increase of hydrate saturation at the same initial porosity and permeability of sandstone. The highest CH4 recovery obtained is 51.6% and 99.4% of CO2 in simulated flue gas is sequestered in the hydrate phase after swapping at 9.2 MPa and 277.15 K. Hydrate saturation was 82.5% and the initial porosity and permeability of sandstone are 25.1% and 49 mD, respectively. With the increase of initial porosity and permeability of sandstone, the CH4 recovery efficiency and the amount of CO2 captured increase when other conditions (the hydrate saturation and reaction time) are similar. For investigating the CH4-flue gas swapping mechanism, a micro-differential scanning calorimetry was used to test the heat changes in the whole reaction. No noticeable endothermic or exothermic phenomenon was detected in the CH4-flue gas swapping, which indicates that CH4 hydrate would form mixed hydrates directly instead of going through a dissociation and reformation process. Based on the observed experimental results, a CH4-flue gas swapping mechanism is proposed and the reaction process is found to be essentially controlled by mass transfer.

Description: Marine methane hydrate in sands has huge potential as an unconventional gas resource; however, no field test of their production potential had been conducted. Here, we report the world’s first offshore methane hydrate production test conducted at the eastern Nankai Trough and show key findings toward future commercial production. Geological analysis indicates that hydrate saturation reaches 80% and permeability in the presence of hydrate ranges from 0.01 to 10 mdarcies. Permeable (1–10 mdarcies) highly hydrate-saturated layers enable depressurization-induced gas production of approximately 20,000 Sm3/D with water of 200 m3/D. Numerical analysis reveals that the dissociation zone expands laterally 25 m at the front after 6 days. Gas rate is expected to increase with time, owing to the expansion of the dissociation zone. It is found that permeable highly hydrate-saturated layers increase the gas–water ratio of the production fluid. The identification of such layers is critically important to increase the energy efficiency and the technical feasibility of depressurization-induced gas production from hydrate reservoirs.

Description: In the colloidal synthesis of iron sulfides, a series of dialkyl disulfides, alkyl thiols, and dialkyl disulfides (allyl, benzyl, tert-butyl, and phenyl) were employed as sulfur sources. Their reactivity was found to tune the phase between pyrite (FeS2), greigite (Fe3S4), and pyrrhotite (Fe7S8). DFT was used to show that sulfur-rich phases were favored when the C–S bond strength was low in the organosulfurs, yet temperature dependent studies and other observations indicated the reasons for phase selectivity were more nuanced; the different precursors decomposed through different reaction mechanisms, some involving the oleylamine solvent. The formation of pyrite from diallyl disulfide was carefully studied as it was the only precursor to yield FeS2. Raman spectroscopy indicated that FeS2 forms directly without an FeS intermediate, unlike most synthetic procedures to pyrite. Diallyl disulfide releases persulfide (S–S)2– due to the lower C–S bond strength relative to the S–S bond strength, as well as facile decomposition in the presence of amines through SN2′ mechanisms at elevated temperatures.

Description: Japanese flounder, Paralichthys olivaceus, is an economically important marine fish species in Asia. A suite of 18 microsatellite markers chosen from published genetic linkage maps was used to carry out parentage assignments of 188 hatchery-reared juveniles from a small number of breeders. The probabilities of exclusion for the 18 microsatellite markers were 0.604–0.913, and the effectiveness of combined probability of exclusion reached 100% when using the eight microsatellite markers with higher Excl 1 probabilities. The cultured and wild stocks (WSs) were differentiated in a release-recapture population based on these markers. Of the 321 recaptured offspring, 28.34% were assigned to their parental pairs in our broodstock, whereas the remaining offspring could not be traced back to a possible sire or dam. Significant reduction in genetic diversity of the cultured stock (CS) had not been found compared with that of the WS. The results suggest that CSs released into the wild will not adversely affect the genetic structure of natural populations. Our results demonstrate that these markers provide an efficient tool for parentage assignments and genetic analysis of Japanese flounder.

Description: A synthesis of the 12,12′-azo-analogue of ritterazine N from hecogenin is reported. Ring contraction of two 6/5 bicyclic ring systems, one trans-fused and another spiro, to 5/5 spiro ring systems is accomplished with excellent stereochemical control. Key transformations include an abnormal Baeyer–Villiger oxidation, a Norrish type I cleavage, an intramolecular dipolar [3 + 2] cycloaddition, and an intramolecular oxymecuration. Failing to uncover the β-OH ketone from the isoxazoline ring, we end up with a synthesis of a cyclic analogue of ritterazine N.

Description: The spatial structure of species is important for their dynamics and evolution, but also for management and conservation. There are numerous ways of inferring spatial structures, and information from multiple methods is becoming more common to examine how different processes shape the spatial structures of species to improve fish management. Here, we investigate the spatial structure of a suite of Baltic Sea fish species based on the following: (i) spatial (presumably neutral) genetic differentiation, reviewed from the literature, and (ii) spatial synchrony in abundance changes from time series of fishery-independent surveys, which we currently find to be underused given the amount of data available. For each of these two methods, species were classified as having a distinct, continuous or no/weak spatial structure. In addition, based on each source of information, we estimated the spatial scale of management units for species. The results show that only among species confined to the coastal zone the two sources of information yielded a congruence of the spatial structure (displaying a continuous spatial structure). In contrast, offshore species show weak spatial genetic structure but stronger spatial structure of synchrony in abundance. Based on this, we suggest that population genetic structure and synchrony in abundance should be used as complementary information as they reflect different spatial processes and suggest that management actions should differ with respect to scale depending on the management targets applied. We propose similar analysis should be applied to areas outside the Baltic Sea, and other stock identification methods, to improve management of fish resources.

Description: Climatic warming is a primary driver of change in ecosystems worldwide. Here, we synthesize responses of species richness and evenness from 187 experimental warming studies in a quantitative meta-analysis. We asked 1) whether effects of warming on diversity were detectable and consistent across terrestrial, freshwater and marine ecosystems, 2) if effects on diversity correlated with intensity, duration, and experimental unit size of temperature change manipulations, and 3) whether these experimental effects on diversity interacted with ecosystem types. Using multilevel mixed linear models and model averaging, we also tested the relative importance of variables that described uncontrolled environmental variation and attributes of experimental units. Overall, experimental warming reduced richness across ecosystems (mean log-response ratio = –0.091, 95% bootstrapped CI: –0.13, –0.05) representing an 8.9% decline relative to ambient temperature treatments. Richness did not change in response to warming in freshwater systems, but was more strongly negative in terrestrial (–11.8%) and marine (–10.5%) experiments. In contrast, warming impacts on evenness were neutral overall and in aquatic systems, but weakly negative on land (7.6%). Intensity and duration of experimental warming did not explain variation in diversity responses, but negative effects on richness were stronger in smaller experimental units, particularly in marine systems. Model-averaged parameter estimation confirmed these main effects while accounting for variation in latitude, ambient temperature at the sites of manipulations, venue (field versus lab), community trophic type, and whether experiments were open or closed to colonization. These analyses synthesize extensive experimental evidence showing declines in local richness with increased temperature, particularly in terrestrial and marine communities. However, the more variable effects of warming on evenness were better explained by the random effect of site identity, suggesting that effects on species’ relative abundances were contingent on local species composition.

Description: Marine plastic debris is a global environmental problem. Surveys have shown that 〈5 mm plastic particles, known as microplastics, are significantly more abundant in surface seawater and on shorelines than larger plastic particles are. Nevertheless, quantification of microplastics in the environment is hampered by a lack of adequate high-throughput methods for distinguishing and quantifying smaller size fractions (〈1 mm), and this has probably resulted in an underestimation of actual microplastic concentrations. Here we present a protocol that allows high-throughput detection and automated quantification of small microplastic particles (20–1000 μm) using the dye Nile red, fluorescence microscopy, and image analysis software. This protocol has proven to be highly effective in the quantification of small polyethylene, polypropylene, polystyrene, and nylon-6 particles, which frequently occur in the water column. Our preliminary results from sea surface tows show a power-law increase in small microplastics (i.e., 〈1 mm) with a decreasing particle size. Hence, our data help to resolve speculation about the “apparent” loss of this fraction from surface waters. We consider that this method presents a step change in the ability to detect small microplastics by substituting the subjectivity of human visual sorting with a sensitive and semiautomated procedure.

Description: The Ignik Sikumi Gas Hydrate Exchange Field Experiment was conducted by ConocoPhillips in partnership with the U.S. Department of Energy, the Japan Oil, Gas and Metals National Corporation, and the U.S. Geological Survey within the Prudhoe Bay Unit on the Alaska North Slope during 2011 and 2012. The primary goals of the program were to (1) determine the feasibility of gas injection into hydrate-bearing sand reservoirs and (2) observe reservoir response upon subsequent flowback in order to assess the potential for C02 exchange for CH4 in naturally occurring gas hydrate reservoirs. Initial modeling determined that no feasible means of injection of pure C02 was likely, given the presence of free water in the reservoir. Laboratory and numerical modeling studies indicated that the injection of a mixture of C02 and N2 offered the best potential for gas injection and exchange. The test featured the following primary operational phases: (1) injection of a gaseous phase mixture of C02, N2, and chemical tracers; (2) flowback conducted at downhole pressures above the stability threshold for native CH4 hydrate; and ( 3) an extended ( 30-days) flowback at pressures near, and then below, the stability threshold of native CH4 hydrate. The test findings indicate that the formation of a range of mixed-gas hydrates resulted in a net exchange of C02 for CH4 in the reservoir, although the complexity of the subsurface environment renders the nature, extent, and efficiency of the exchange reaction uncertain. The next steps in the evaluation of exchange technology should feature multiple well applications; however, such field test programs will require extensive preparatory experimental and numerical modeling studies and will likely be a secondary priority to further field testing of production through depressurization. Additional insights gained from the field program include the following: (1) gas hydrate destabilization is self-limiting, dispelling any notion of the potential for uncontrolled destabilization; (2) gas hydrate test wells must be carefully designed to enable rapid remediation of wellbore blockages that will occur during any cessation in operations; (3) sand production during hydrate production likely can be managed through standard engineering controls; and ( 4) reservoir heat exchange during depressurization was more favorable than expected-mitigating concerns for near-wellbore freezing and enabling consideration of more aggressive pressure reduction.

Description: Fisheries advice is based on demographic calculations, which assume that density-dependent processes regulating recruitment occur only in early life. This assumption is challenged by laboratory and lake studies and some recent indications from marine systems that demonstrate density-dependent regulation late in life. By accounting for spatial dynamics of a population, something that has previously been ignored in models of fish, we show that density-dependent regulation is determined by the size of the habitat: in small habitats, for example small lakes, regulation occurs late in life, while it can occur early in large habitats. When regulation happens late in life, fisheries yield is maximized by exploitation of mainly juvenile fish, while exploiting mature fish maximizes yield if regulation happens early. We review and interpret observations of density dependence in the light of the theory. Our results challenge the current assumption that density dependence always occurs early in life and highlights the need for an increased understanding of density-dependent processes. This can only come about by a change of focus from determining stock-recruitment relationships towards understanding when and how density-dependent regulation occurs in nature.

Description: The spatial structure of species is important for their dynamics and evolution, but also for management and conservation. There are numerous ways of inferring spatial structures, and information from multiple methods is becoming more common to examine how different processes shape the spatial structures of species to improve fish management. Here, we investigate the spatial structure of a suite of Baltic Sea fish species based on the following: (i) spatial (presumably neutral) genetic differentiation, reviewed from the literature, and (ii) spatial synchrony in abundance changes from time series of fishery‐independent surveys, which we currently find to be underused given the amount of data available. For each of these two methods, species were classified as having a distinct, continuous or no/weak spatial structure. In addition, based on each source of information, we estimated the spatial scale of management units for species. The results show that only among species confined to the coastal zone the two sources of information yielded a congruence of the spatial structure (displaying a continuous spatial structure). In contrast, offshore species show weak spatial genetic structure but stronger spatial structure of synchrony in abundance. Based on this, we suggest that population genetic structure and synchrony in abundance should be used as complementary information as they reflect different spatial processes and suggest that management actions should differ with respect to scale depending on the management targets applied. We propose similar analysis should be applied to areas outside the Baltic Sea, and other stock identification methods, to improve management of fish resources.

Description: We report U–Pb zircon ages of c. 700–550 Ma, 262–220 Ma, 47–38 Ma and 15–14 Ma from amphibolites on Naxos Island in the Aegean extensional province of Greece. The zircon has complex internal structures. Based on cathodoluminescence response, zoning and crosscutting relationships a minimum of four zircon growth stages are identified: inherited core, magmatic core, inner metamorphic (?) rim and an outer metamorphic rim. Trace element compositions of the amphibolites suggest igneous differentiation and crustal assimilation. Zircon solubility as a function of saturation temperatures, Zr content and melt composition indicates that the zircon did not originally crystallize in the mafic bodies but was inherited from felsic precursor rocks, and subsequently assimilated into the mafic intrusives during emplacement. Zircon inheritance is corroborated by the complex, xenocrystic nature of the zircon in one sample. Ages of c. 700–550 Ma and 262–220 Ma are assigned to inherited zircon. Available geochemical data suggest that the 15–14 Ma metamorphic rims grew in situ in the amphibolites, corresponding to a high-grade metamorphic event at this time. However, the geochemical data cannot conclusively establish if the c. 40 Ma zircon rims also grew in situ, or whether they were inherited along with the xenocrystic cores. Two scenarios for emplacement of the mafic intrusives are discussed: (i) Intrusion during late-Triassic to Jurassic ocean basin development of the Aegean realm, in which case the 40 Ma zircon rims would have grown in situ, and (ii) emplacement in the Miocene as a result mafic underplating during large-scale extension. In this case, only the 15–14 Ma metamorphic outer rims would have formed in situ in the amphibolitic host rocks.

Description: Managing fisheries presents trade-offs between objectives, for example yields, profits, minimizing ecosystem impact, that have to be weighed against one another. These trade-offs are compounded by interacting species and fisheries at the ecosystem level. Weighing objectives becomes increasingly challenging when managers have to consider opposing objectives from different stakeholders. An alternative to weighing incomparable and conflicting objectives is to focus on win–wins until Pareto efficiency is achieved: a state from which it is impossible to improve with respect to any objective without regressing at least one other. We investigate the ecosystem-level efficiency of fisheries in five large marine ecosystems (LMEs) with respect to yield and an aggregate measure of ecosystem impact using a novel calibration of size-based ecosystem models. We estimate that fishing patterns in three LMEs (North Sea, Barents Sea and Benguela Current) are nearly efficient with respect to long-term yield and ecosystem impact and that efficiency has improved over the last 30 years. In two LMEs (Baltic Sea and North East US Continental Shelf), fishing is inefficient and win–wins remain available. We additionally examine the efficiency of North Sea and Baltic Sea fisheries with respect to economic rent and ecosystem impact, finding both to be inefficient but steadily improving. Our results suggest the following: (i) a broad and encouraging trend towards ecosystem-level efficiency of fisheries; (ii) that ecosystem-scale win–wins, especially with respect to conservation and profits, may still be common; and (iii) single-species assessment approaches may overestimate the availability of win–wins by failing to account for trade-offs across interacting species.

Description: Ecological studies based on time-series often investigate community changes centered on species abundance or biomass but rarely expose the consequential functional aspects underlying such changes. Functional diversity measures have proven to be more accurate predictors for ecosystem functioning than traditional taxonomic approaches and hence gained much attention. There are only limited studies available that analyse the functional implications behind decadal changes of entire communities. We studied zoobenthic communities of two habitats, sheltered and exposed, of a coastal system subject to contrasting changes in community composition over the past four decades. Besides eutrophication and climate-related impacts, the system has been invaded by a non-native polycheate Marenzelleria spp., adding altered functional properties to the communities. The functional dispersion (FDis) metric was used as a measure for comparing the functional diversity of the contrasting habitats, with special focus on the role of Marenzelleria for the entire communities. We highlight changes in the functional identity of the communities, expressed as community-weighted means of trait expression (CWM), using multivariate techniques, and investigate the relationship between taxonomic and functional changes. Despite contrasting community developments in the two habitats, with characteristics traditionally suggesting different environmental quality, we found that the FDis in both habitats remained similar and increased with the introduction of Marenzelleria. Although showing maintained functional diversity across time and space, the functional identity (CWM) of communities changed irrespective of taxonomical differences. Examples include inter alia alterations in palatability proxies, feeding position and sediment transportation types, indicating changed functionality of zoobenthos in coastal systems. We show, when focussing on qualitative functional changes of communities, it is important to evaluate the underlying functional identity, and not only rely on measures of the diversity of functions per se, as the quality indication of expressed functional traits can be concealed when using multi-functionality approaches.

Description: The advent of genomic-, transcriptomic- and proteomic-based approaches has revolutionized our ability to describe marine microbial communities, including biogeography, metabolic potential and diversity, mechanisms of adaptation, and phylogeny and evolutionary history. New interdisciplinary approaches are needed to move from this descriptive level to improved quantitative, process-level understanding of the roles of marine microbes in biogeochemical cycles and of the impact of environmental change on the marine microbial ecosystem. Linking studies at levels from the genome to the organism, to ecological strategies and organism and ecosystem response, requires new modelling approaches. Key to this will be a fundamental shift in modelling scale that represents micro-organisms from the level of their macromolecular components. This will enable contact with omics data sets and allow acclimation and adaptive response at the phenotype level (i.e. traits) to be simulated as a combination of fitness maximization and evolutionary constraints. This way forward will build on ecological approaches that identify key organism traits and systems biology approaches that integrate traditional physiological measurements with new insights from omics. It will rely on developing an improved understanding of ecophysiology to understand quantitatively environmental controls on microbial growth strategies. It will also incorporate results from experimental evolution studies in the representation of adaptation. The resulting ecosystem-level models can then evaluate our level of understanding of controls on ecosystem structure and function, highlight major gaps in understanding and help prioritize areas for future research programs. Ultimately, this grand synthesis should improve predictive capability of the ecosystem response to multiple environmental drivers.

Description: Despite considerable progress in the production of alternative diets, small concentrations of antinutrients remain common in aquaculture nutrition, resulting in a perpetual limitation with regard to the inclusion of plant ingredients in aquafeeds. These compounds are known to impair the general performance of fish when fed for a prolonged period of time, potentially affecting the animal's susceptibility to stress, too. Therefore, a 12-week feeding trial was conducted to examine the chronic effects of purified rapeseed protein concentrate (RPC), containing low concentrations of glucosinolates and phytic acid, on the relative expression of multiple target genes in the liver of juvenile turbot (Psetta maxima, L.). Our results revealed divergent patterns of gene expression, suggesting different coping strategies dependent on the grade of RPC substitution. Data implies increased metabolic rate of turbot fed a 33% RPC-substituted diet due to an upregulation of cytochrome c oxidase mRNA, accompanied by minor adjustments in metabolic pathways. While no signs of reduced welfare were found, data adumbrate a beneficial hormetic reaction. In the highest treatment level (66% RPC), diminished fish condition and reduced growth performance coincided with a downregulation of insulin-like growth factor I, further indicating a potential impaired resistance to stress. An additional downregulation of transferrin hints towards an increased liability to bacterial infections.

Description: This paper proposes improved guidelines for dissolved organic matter (DOM) isolation by solid phase extraction (SPE) with a styrene-divinylbenzene copolymer (PPL) sorbent, which has become an established method for the isolation of DOM from natural waters, because of its ease of application and appreciable carbon recovery. Suwannee River water was selected to systematically study the effects of critical SPE variables such as loading mass, concentration, flow rate, and up-scaling on the extraction selectivity of the PPL sorbent. High-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and proton nuclear magnetic resonance (H-1 NMR) spectroscopy were performed to interpret the DOM chemical space of eluates, as well as permeates and-wash liquids with molecular resolution. Up to 89% dissolved organic carbon (DOC) recovery was obtained with a DOC/PPL mass ratio of 1:800 at a DOC concentration of 20 mg/L. With the 0 application of larger loading volumes, low proportions of highly oxygenated compounds were retained on the PPL sorbent. The effects of the flow rate on the extraction selectivity of the sorbent were marginal. Up-scaling had a limited effect on the extraction selectivity with the exception of increased self-esterification with a methanol solvent, resulting in methyl ester groups. Furthermore, the SPE/PPL extract exhibited highly authentic characteristics in comparison with original water and reverse osmosis samples. These findings will be useful for reproducibly isolating DOM with representative molecular compositions from various sources and concentrations and minimizing potential inconsistencies among interlaboratory comparative studies.

Description: To estimate the anthropogenic contribution to climate signals in the recent past and future decades implies a certain degree of confidence in both understanding and simulating natural internal variability at interdecadal time scales. If we are to embark on the challenge of decadal prediction, we must be able to mechanistically attribute events to known processes and phenomena, and reproduce their features and statistics within our models. To date, models have succeeded in reproducing only partially spatial patterns, statistics and climatic impacts of interdecadal modes of variability. Reasons for the partial success and agreement among models are to be attributed to the short observational record, the different and complex flavours of coupling between the many subcomponents of the climate system, and the present inability to resolve all climate processes. At an even more fundamental level, this difficulty is aggravated by the limited understanding of the physical mechanisms involved. Here, we review the proposed mechanisms giving rise to interdecadal climate variability, we discuss the hypotheses explaining the main interdecadal modes of variability, and present an overview on the ability and level of agreement in their simulation by the latest generation of coupled climate models. To achieve any progress, the modeling community should focus on both improving the representation and parameterization of key ocean physical processes and obtaining a firmer grasp on the physical mechanisms generating the variability. Both goals can benefit from process studies, intercomparisons with perturbation experiments to study model's sensitivities, and the use of a hierarchy of climate models.

Description: The first total synthesis and structure revision of (−)-11β-hydroxycurvularin (1b), a macrolide possessing a β-hydroxyketone moiety, were accomplished. The β-hydroxyketone moiety in this natural product was introduced by cleavage of the N–O bond in an isoxazoline ring that was formed diastereoselectively in a 1,5-remote stereocontrolled fashion by employing intramolecular nitrile oxide cycloaddition

Description: The exploration and proposed mining of sulfide massive deposits in deep-sea environments and increased use deep-sea tailings placement (DSTP) in coastal zones has highlighted the need to better understand the fate and effects of mine-derived materials in marine environments. Metal sulfide ores contain high concentrations of metal(loid)s, of which a large portion exist in highly mineralized or sulfidised forms and are predicted to exhibit low bioavailability. In this study, sediments were spiked with a range of natural sulfide minerals (including chalcopyrite, chalcocite, galena, sphalerite) to assess the bioavailability and toxicity to benthic invertebrates (bivalve survival and amphipod survival and reproduction). The metal sulfide phases were considerably less bioavailable than metal contaminants introduced to sediment in dissolved forms, or in urban estuarine sediments contaminated with mixtures of metal(loid)s. Compared to total concentrations, the dilute-acid extractable metal(loid) (AEM) concentrations, which are intended to represent the more oxidized and labile forms, were more effective for predicting the toxicity of the sulfide mineral contaminated sediments. The study indicates that sediment quality guidelines based on AEM concentrations provide a useful tool for assessing and monitoring the risk posed by sediments impacted by mine-derived materials in marine environments.

Description: The guest-exchange method (or replacement) for methane production from gas hydrates has recently received attention because it can be used for both carbon dioxide sequestration and methane production. The structure of gas hydrates is maintained as a structure I (sI) hydrate while methane molecules are exchanged with carbon dioxide. In this study, CH4 + CO2 mixed gas hydrates were examined under terahertz light at various temperatures to simulate CH4–CO2 exchange reactions. Each gas hydrate composition examined was a representative composition at each step of the exchange reaction. The molecular composition was also accurately analyzed by gas chromatography. Refractive indices calculated by the terahertz time-domain spectroscopy (THz-TDS) of gas hydrate samples were correlated to the guest composition, and this novel method was proven to be used to quantify the extent of replacement via optical constant. Furthermore, changes in the water framework from the sI hydrate to ice using THz-TDS were investigated with an increasing temperature. Overall, this study reveals the process of guest exchange and phase transition from a gas hydrate to ice via the optical properties in the terahertz region, and it offers a powerful tool in gas hydrate production.

Description: The geological development of the Fogo island volcano commenced in the early Quaternary, and much later during the Last Glacial stage this involved a mega-scale lateral collapse of the former edifice. This later event created a large caldera-like landform open to the east, the floor of which is known as the Chã, and subsequently within this a strato-volcanic cone has grown. The last phase of volcanic activity started in late 2014 and persisted for 77 days. It had a devastating impact on the lives of the 1000 plus people who were living within the ‘caldera’, since two large villages and a smaller one were each totally destroyed in a matter of days by the advancing lavas. In addition, large areas of cultivated land, upon which the inhabitants were dependent for their livelihood, were enveloped by lava. The eruption proved to be of a greater magnitude than the immediately preceding one of 1995, when a mass evacuation was necessary but as only a few buildings were affected, resettlement followed. Unfortunately the much greater devastation to the human environment makes it doubtful whether any significant resettlement will be possible after the 2014–2015 event.

Description: Implantable endovascular devices such as bare metal, drug eluting, and bioresorbable stents have transformed interventional care by providing continuous structural and mechanical support to many peripheral, neural, and coronary arteries affected by blockage. Although effective in achieving immediate restoration of blood flow, the long-term re-endothelialization and inflammation induced by mechanical stents are difficult to diagnose or treat. Here we present nanomaterial designs and integration strategies for the bioresorbable electronic stent with drug-infused functionalized nanoparticles to enable flow sensing, temperature monitoring, data storage, wireless power/data transmission, inflammation suppression, localized drug delivery, and hyperthermia therapy. In vivo and ex vivo animal experiments as well as in vitro cell studies demonstrate the previously unrecognized potential for bioresorbable electronic implants coupled with bioinert therapeutic nanoparticles in the endovascular system.

Description: The shrinking-core model of the formation of gas hydrates from ice spheres with well-defined geometry gives experimental access to the gas permeation in bulk hydrates which is relevant to their use as energy storage materials, their exploitation from natural resources, as well as to their role in flow assurance. Here we report on a new approach to model CO2 clathration experiments in the temperature range from 230 to 272 K. We develop a comprehensive description of the gas permeation based on the diffusion along the network of polyhedral cages, some of them being empty. Following earlier molecular dynamics simulation results, the jump from a cage to one of its empty neighbors is assumed to proceed via a “hole-in-cage-wall” mechanism involving water vacancies in cage walls. The rate-limiting process in the investigated temperature range can be explained by the creation of water-vacancy-interstitial pairs. The gas diffusion leads to a time-dependent cage filling which decreases across the hydrate layer with the distance from the particle surface. The model allows a prediction of the time needed for a complete conversion of ice spheres into clathrate as well as the time needed for a full equilibration of the cage fillings. The findings essentially support our earlier results obtained in the framework of a purely phenomenological permeation model in terms of the overall transformation kinetics, yet it provides for the first time insight into the cage equilibration processes. The diffusion of CO2 molecules through bulk hydrate is found to be about three to four times faster in comparison with the CH4 case.

Description: The herbal remedy, milk thistle (Silybum marianum), has been used in traditional medicine for various liver, kidney, and gall bladder ailments. For over a decade, our research group has been investigating the flavonolignans obtained from this medicinal herb for cancer chemoprevention and hepatoprotection.[1–6] Recently, we extended our studies toward examining the diversity as well as distribution patterns of fungal endophytes in leaves, stem, and roots of milk thistle.[7] These fungi inhabit the internal living tissues of the host plants asymptomatically, though they may also cause disease over time.[8] In addition to the phylogenetic profiling of these endophytes, a series of fungal extracts were also examined for chemical composition. Although the plant–endophyte relationship may ormay not be mutualistic, the compounds produced by some endophytes could play a role in the growth and survival of the host. In a previous study, Penicillium restrictum, isolated from milk thistle, yielded promising secondary metabolites.[9] Hence, in pursuit of interesting chemistry, a related monoverticillate endophytic Penicillium sp. was explored.

Description: Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Description: Viruses play important roles in microbial ecology and some infectious diseases, but relatively little is known about the concentrations, sources, transformation, and fate of viruses in the atmosphere. We have measured total airborne concentrations of virus-like and bacterium-like particles (VLPs between 0.02 and 0.5 μm in size and BLPs between 0.5 and 5 μm) in nine locations: a classroom, a daycare center, a dining facility, a health center, three houses, an office, and outdoors. Indoor concentrations of both VLPs and BLPs were ∼105 particles m–3, and the virus:bacteria ratio was 0.9 ± 0.1 (mean ± standard deviation across different locations). There were no significant differences in concentration between different indoor environments. VLP and BLP concentrations in outdoor air were 2.6 and 1.6 times higher, respectively, than in indoor air. At the single outdoor site, the virus:bacteria ratio was 1.4.

Description: Two discontinuous tephra layers were discovered at Burney Spring Mountain, northern California. Stratigraphic relationships suggest that they are two distinct primary fall tephras. The geochemistries of these tephras from electron probe microanalysis were compared with those of known layers found in the area to test for potential correlations, using clustering analysis on geochemistry. In most cases, geochemical data from a tephra layer can be assigned to a single cluster, but in some cases the analyses are spread over several clusters. This spreading is a direct result of mixing and reworking of several tephra layers. The mixing, in turn, appears to be related to the influence of wind in a marshy environment.

Description: Stock‐based and ecosystem‐based indicators are used to provide a new diagnosis of the fishing impact and environmental status of European seas. In the seven European marine ecosystems covering the Baltic and the North‐east Atlantic, (i) trends in landings since 1950 were examined; (ii) syntheses of the status and trends in fish stocks were consolidated at the ecosystem level; and (iii) trends in ecosystem indicators based on landings and surveys were analysed. We show that yields began to decrease everywhere (except in the Baltic) from the mid‐1970s, as a result of the over‐exploitation of some major stocks. Fishermen adapted by increasing fishing effort and exploiting a wider part of the ecosystems. This was insufficient to compensate for the decrease in abundance of many stocks, and total landings have halved over the last 30 years. The highest fishing impact took place in the late 1990s, with a clear decrease in stock‐based and ecosystem indicators. In particular, trophic‐based indicators exhibited a continuous decreasing trend in almost all ecosystems. Over the past decade, a decrease in fishing pressure has been observed, the mean fishing mortality rate of assessed stocks being almost halved in all the considered ecosystems, but no clear recovery in the biomass and ecosystem indicators is yet apparent. In addition, the mean recruitment index was shown to decrease by around 50% in all ecosystems (except the Baltic). We conclude that building this kind of diagnosis is a key step on the path to implementing an ecosystem approach to fisheries management.

Description: Numerical tools are essential for the prediction and evaluation of conventional hydrocarbon reservoir performance. Gas hydrates represent a vast natural resource with a significant energy potential. The numerical codes/tools describing processes involved during the dissociation (induced by several methods) for gas production from hydrates are powerful, but they need validation by comparison to empirical data to instill con fidence in their predictions. In this study, we successfully reproduce experimental data of hydrate dissociation using the TOUGH+HYDRATE (T+H) code. Methane(CH4)hydrate growth and dissociation in partially water- and gas-saturated Bentheim sandstone were spatially resolved using Magnetic Resonance Imaging (MRI), which allows the in situ monitoring of saturation and phase transitions. All the CH4 that had been initially converted to gas hydrate was recovered during depressurization. The physical system was reproduced numerically, usingboth a simplified 2D model and a 3D grid involving complex Voronoi elements. We modeled dissociation using both the equilibrium and the kinetic reaction options in T+H, and we used a range of kinetic parameters for sensitivity analysis and curve fitting. We successfully reproduced the experimental results, which confirmed the empirical data that demonstrated that heattransport was the limiting factor during dissociation. Dissociation was more sensitive to kinetic parameters than anticipated, which indicates that kinetic limitations may be important in short-term core studies and a necessity in such simulations. This is the first time T+H has been used to predict empirical nonmonotonic dissociation behavior, where hydrate dissociation and reformation occurred as parallel events.

Description: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used widely to analyse single volcanic glass shards from Quaternary tephra deposits for stratigraphic correlation. As yet, no generally accepted protocol for these analyses exists and published methods report significant differences in crater size and calibration strategies. Using Ca as the ‘internal standard’ (CaI.S.), and not SiI.S., for the analysis of rhyolitic glass can cause significant problems, because of ablation of (i) Ca-rich phenocrysts, notably ‘ubiquitous’ plagioclase, but also calcic-amphibole, apatite and allanite or (ii) mounting epoxy resin which can contribute to the Ca internal standard signal. Using CaI.S. can cause underreporting of many elements which concentrate in Ca-rich phenocrysts, making their ablation difficult to recognize, but when using SiI.S., no such underreporting occurs. Additionally, larger ablation craters (50mm diameter) potentially incorporate even small volumes of phenocryst material, whereas smaller craters (〈20mm diameter) more frequently miss phenocrysts. Thus, for the LA-ICP-MS analysis of rhyolitic glass shards, smaller ablation craters should be employed and calibrated using SiI.S., allowing recognition and removal of analyses incorporating Ca-rich phenocrysts and avoiding issues related to the ablation of the mounting resin.

Description: The current difficulty in visualizing the true extent of malignant brain tumors during surgical resection represents one of the major reasons for the poor prognosis of brain tumor patients. Here, we evaluated the ability of a hand-held Raman scanner, guided by surface-enhanced Raman scattering (SERS) nanoparticles, to identify the microscopic tumor extent in a genetically engineered RCAS/tv-a glioblastoma mouse model. In a simulated intraoperative scenario, we tested both a static Raman imaging device and a mobile, hand-held Raman scanner. We show that SERS image-guided resection is more accurate than resection using white light visualization alone. Both methods complemented each other, and correlation with histology showed that SERS nanoparticles accurately outlined the extent of the tumors. Importantly, the hand-held Raman probe not only allowed near real-time scanning, but also detected additional microscopic foci of cancer in the resection bed that were not seen on static SERS images and would otherwise have been missed. This technology has a strong potential for clinical translation because it uses inert gold-silica SERS nanoparticles and a hand-held Raman scanner that can guide brain tumor resection in the operating room.

Description: Electrolytes can thermodynamically inhibit clathrate hydrate formation by lowering the activity of water in the surrounding liquid phase, causing the hydrates to form at lower temperatures and higher pressures compared to their formation in pure water. However, it has been reported that some thermodynamic hydrate inhibitors (THIs), when doped at low concentrations, could enhance the rate of gas hydrate formation. We here report a systematic study of model natural gas (a mixture of 90% methane and 10% propane) hydrate formation in strong monovalent salt solutions in a broad range of concentrations, using a high pressure automated lag time apparatus (HP-ALTA). HP-ALTA can apply a large number (〉100) of cooling ramps to a sample and construct probability distributions of gas hydrate formation for each sample. The probabilistic interpretation of data enables us to mitigate the stochastic variation inherent in the nucleation probability distributions and facilitates meaningful comparison among different samples. The electrolytes used in this work are lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), sodium chloride (NaCl), sodium bromide (NaBr), sodium iodide (NaI), potassium chloride (KCl), potassium bromide (KBr), and potassium iodide (KI). We found that (1) some salts may act as kinetic hydrate promoters at low concentrations; (2) the width of the probability distributions (stochasticity) of natural gas hydrate formation in these salt solutions was significantly narrower than that in pure water. To gain further insight, we extended the study of the solutions of the same nine salts to the formation of ice and model tetrahydrofuran (THF) hydrate for comparison.

Description: Landscape connectivity can increase the capacity of communities to maintain their function when environments change by promoting the immigration of species or populations with adapted traits. However, high immigration may also restrict fine tuning of species compositions to local environmental conditions by homogenizing the community. Here we demonstrate that dispersal generates such a tradeoff between maximizing local biomass and the capacity of model periphyton metacommunities to recover after a simulated heat wave. In non-disturbed metacommunities, dispersal decreased the total biomass by preventing differentiation in species composition between the local patches making up the metacommunity. On the contrary, in metacommunities exposed to a realistic summer heat wave, dispersal promoted recovery by increasing the biomass of heat tolerant species in all local patches. Thus, the heat wave reorganized the species composition of the metacommunities and after an initial decrease in total biomass by 38.7%, dispersal fueled a full recovery of biomass in the restructured metacommunities. Although dispersal may decrease equilibrium biomass, our results highlight that connectivity is a key requirement for the response diversity that allows ecological communities to adapt to climate change through species sorting.

Description: This paper focuses on the marine foundation eelgrass species, Zostera marina, along a gradient from the northern Baltic Sea to the north-east Atlantic. This vast region supports a minimum of 1480 km2 eelgrass (maximum 〉2100 km2), which corresponds to more than four times the previously quantified area of eelgrass in Western Europe. Eelgrass meadows in the low salinity Baltic Sea support the highest diversity (4–6 spp.) of angiosperms overall, but eelgrass productivity is low (〈2 g dw m-2 d-1) and meadows are isolated and genetically impoverished. Higher salinity areas support monospecific meadows, with higher productivity (3–10 g dw m-2 d-1) and greater genetic connectivity. The salinity gradient further imposes functional differences in biodiversity and food webs, in particular a decline in number, but increase in biomass of mesograzers in the Baltic. Significant declines in eelgrass depth limits and areal cover are documented, particularly in regions experiencing high human pressure. The failure of eelgrass to re-establish itself in affected areas, despite nutrient reductions and improved water quality, signals complex recovery trajectories and calls for much greater conservation effort to protect existing meadows. The knowledge base for Nordic eelgrass meadows is broad and sufficient to establish monitoring objectives across nine national borders. Nevertheless, ensuring awareness of their vulnerability remains challenging. Given the areal extent of Nordic eelgrass systems and the ecosystem services they provide, it is crucial to further develop incentives for protecting them.

Description: Molybdenum isotopes are increasingly widely applied in Earth Sciences. They are primarily used to investigate the oxygenation of Earth's ocean and atmosphere. However, more and more fields of application are being developed, such as magmatic and hydrothermal processes, planetary sciences or the tracking of environmental pollution. Here, we present a proposal for a unifying presentation of Mo isotope ratios in the studies of mass-dependent isotope fractionation. We suggest that the Mo-98/95 of the NIST SRM 3134 be defined as +0.25. The rationale is that the vast majority of published data are presented relative to reference materials that are similar, but not identical, and that are all slightly lighter than NIST SRM 3134. Our proposed data presentation allows a direct first-order comparison of almost all old data with future work while referring to an international measurement standard. In particular, canonical Mo-98/95 values such as +2.3 parts per thousand for seawater and -0.7 parts per thousand for marine Fe-Mn precipitates can be kept for discussion. As recent publications show that the ocean molybdenum isotope signature is homogeneous, the IAPSO ocean water standard or any other open ocean water sample is suggested as a secondary measurement standard, with a defined Mo-98/95 value of +2.34 +/- 0.10 parts per thousand (2s).

Description: This study investigated growth, condition and development of American eels Anguilla rostrata that were introduced into a European river to estimate their competitive potential in a non-native habitat. Results demonstrate that A. rostrata develops normally in European waters and successfully competes with the native European eel Anguilla anguilla. In addition, A. rostrata appears to be more susceptible to the Asian swimbladder nematode Anguillicola crassus than A. anguilla and could support the further propagation of this parasite. Detected differences in fat content and gonad mass between Anguilla species are assumed to reflect species-specific adaptations to spawning migration distances. This study indicates that A. rostrata is a potential competitor for the native fauna in European fresh waters and suggests strict import regulations to prevent additional pressure on A. anguilla and a potential further deterioration of its stock situation.

Description: Ecosystem functioning is affected by horizontal (within trophic groups) and vertical (across trophic levels) biodiversity. Theory predicts that the effects of vertical biodiversity depend on consumer specialization. In a microcosm experiment, we investigated ciliate consumer diversity and specialization effects on algal prey biovolume, evenness and composition, and on ciliate biovolume production. The experimental data was complemented by a process-based model further analyzing the ecological mechanisms behind the observed diversity effects. Overall, increasing consumer diversity had no significant effect on prey biovolume or evenness. However, consumer specialization affected the prey community. Specialist consumers showed a stronger negative impact on prey biovolume and evenness than generalists. The model confirmed that this pattern was mainly driven by a single specialist with a high per capita grazing rate, consuming the two most productive prey species. When these were suppressed, the prey assemblage became dominated by a less productive species, consequently decreasing prey biovolume and evenness. Consumer diversity increased consumer biovolume, which was stronger for generalists than for specialists and highest in mixed combinations, indicating that consumer functional diversity, i.e. more diverse feeding strategies, increased resource use efficiency. Overall, our results indicate that consumer diversity effects on prey and consumers strongly depend on species-specific growth and grazing rates, which may be at least equally important as consumer specialization in driving consumer diversity effects across trophic levels.

Description: We compared the development and fatty acid content of the harpacticoid copepods Tachidius discipes and Tisbe sp. fed with different microalgal species (Dunaliella tertiolecta, Rhodomonas sp., Phaeodactylum tricornutum, Isochrysis galbana and a concentrate of Pavlova sp.), which differed in cell size and fatty acid composition. Tisbe could develop in 11 days with every alga to the same average stage, whereas Tachidius developed poorly when fed with Isochrysis and Dunaliella. Feeding with Phaeodactylum resulted in a fast development of both copepods at low algal concentrations. However, reproduction was higher with Rhodomonas as food than with the other algae. Fatty acid compositions of copepods were influenced by their food source, but both were able to convert docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) from precursors. Tachidius fed with Rhodomonas or Phaeodactylum was closest to the DHA/EPA/arachidonic acid (ARA) ratio of 10 : 5 : 1 considered optimal for some marine fish larvae. Tachidius showed similar development and reproduction capacity as Tisbe, but requested higher absolute fatty acid contents in the diet. Tisbe was superior in the utilization of bacteria as additional food source and the bioconversion of precursor fatty acids. Phaeodactylum and Rhodomonas are recommendable food sources for both copepod species, but Phaeodactylum is more easily cultured.

Description: Four primary glass populations, well defined by their Sr, Ba and Y concentrations, occur in the Youngest Toba Tuff (YTT), which was deposited during a Supereruption of the Toba caldera complex in northern Sumatra 75 ka. Average concentrations of major and trace elements indicate a coherent, systematic Variation of glass composition across populations. No clear pattern in the areal distribution of these four glass groups can be discerned. The multiple glass populations of the YTT easily distinguish it from the single homogeneous glass population of the Middle Toba Tuff (~500 ka), as represented by its basal vitrophyre, and that of the Oldest Toba Tuff (~800 ka), as represented by ash Layer D at the Ocean Drilling Program site 758 in the Indian Ocean.

Description: Climate change will increase both average temperatures and extreme summer temperatures. Analyses of the fitness consequences of climate change have generally omitted negative fitness and population declines associated with heat stress. Here, we examine how seasonal and interannual temperature variability will impact fitness shifts of ectotherms from the past (1961–1990) to future (2071–2100), by modelling thermal performance curves (TPCs) for insect species across latitudes. In temperate regions, climate change increased the length of the growing season (increasing fitness) and increased the frequency of heat stress (decreasing fitness). Consequently, species at mid-latitudes (20–40°) showed pronounced but heterogeneous responses to climate change. Fitness decreases for these species were accompanied by greater interannual variation in fitness. An alternative TPC model and a larger data set gave qualitatively similar results. How close maximum summer temperatures are to the critical thermal maximum of a species – the thermal buffer – is a good predictor of the change in mean fitness expected under climate change. Thermal buffers will decrease to near or below zero by 2100 for many tropical and mid-latitude species. Our forecasts suggest that mid-latitude species will be particularly susceptible to heat stress associated with climate change due to temperature variation

Description: Abstract Aims Bacterially induced calcium carbonate precipitation from various isolates was investigated aiming at developing an environmentally friendly technique for ornamental stone protection and restoration. Methods and Results Microorganisms isolated from stone samples and identified using 16S rDNA and biochemical tests promoted calcium carbonate precipitation in solid and novel liquid growth media. Biomineral morphology was studied on marble samples with scanning electron microscopy. Most isolates demonstrated specimen weight increase, covering partially or even completely the marble surfaces mainly with vaterite. The conditions under which vaterite precipitated and its stability throughout the experimental runs are presented. Conclusions A growth medium that facilitated bacterial growth of different species and promoted biomineralization was formulated. Most isolates induced biomineralization of CaCO3. Microorganisms may actually be a milestone in the investigation of vaterite formation facilitating our understanding of geomicrobiological interactions. Pseudomonas, Pantoea and Cupriavidus strains could be candidates for bio‐consolidation of ornamental stone protection. Significance and Impact of the Study Characterization of biomineralization capacity of different bacterial species improves understanding of the bacterially induced mineralization processes and enriches the list of candidates for bio‐restoration applications. Knowledge of biomineral morphology assists in differentiating mineral from biologically induced precipitates.

Description: Consumer preference for natural food ingredients has increased in recent decades, and the natural food colorant market has grown to over one billion dollars annually. A variety of red, orange, and yellow natural colorants are approved and in use, but there still exists a lack of available blue and purple natural colorant options. The occurrence of blue colored compounds in the natural world is relatively rare. The isolation, identification, and characterization of natural blue and purple pigments obtained from underexplored natural sources such as from obscure terrestrial organisms and marine microorganisms will be discussed.

Description: Understanding the ecological mechanisms that underlie species diversity decline in response to environmental change has become an urgent objective in current ecological research. Not only direct (lethal) effects on single species but also indirect effects altering biotic interactions between species within and across trophic levels comprise the driving force of ecosystem change. In an experimental marine benthic microalgae–grazer system we tested for indirect effects of moderate temperature change on algal diversity by manipulation of temperature, nutrient supply and grazer density. In our model system warming did not exert indirect effects on microalgal diversity via effects on resource competition. However, moderate warming strengthened consumer control and thereby indirectly affected algal community structure which ultimately resulted in decreased diversity. Only in low temperature and low nutrient regimes did the antagonizing mechanisms of bottom–up and top–down regulation establish a balancing effect on algal diversity within 29 days (corresponding to 15–29 algae generations). Effects of thermal habitat change did not appear before 9–18 algae generations, which points to the relevance of longer-term experiments and ecological monitoring in order to separate transient biotic responses and subtle changes of community dynamics in consequence to global change.

Description: Individual migration behaviour during the juvenile and adult life phase of the anadromous twaite shad Alosa fallax in the Elbe estuary was examined using otolith Sr:Ca and Ba:Ca profiles. Between hatching and the end of the first year of life, juveniles showed two migration patterns. Pattern one exhibited a single downstream migration from fresh water to the sea with no return into fresh water. In contrast, pattern two showed a first migration into the sea, then a return into fresh water and, finally, a second downstream migration into marine water. This first report of migration plasticity for A. fallax points to different exposure times to estuarine threats depending on the migration strategy. In adults, high Sr:Ca and low Ba:Ca in the majority of individuals confirmed prior reports of a primarily marine habitat use. Patterns reflecting spawning migrations were rarely observed on otoliths, possibly due to the short duration of visits to fresh water.

Description: Two new natural products, 3 and 4, and their predecessor 7-isocyanoisoneoamphilecta-1(14),15-diene (2), of the rare isoneoamphilectane class of marine diterpenes, along with the known amphilectane diterpenes 6–8, were isolated from the n-hexane extract of the marine sponge Svenzea flava collected at Great Inagua Island, Bahamas. The molecular structures of compounds 3 and 4 were established by spectroscopic (1D/2D NMR, IR, UV, HRMS) methods and confirmed by a series of chemical correlation studies. In a first ever case study of the assignment of the absolute configuration of a molecule based on the isoneoamphilectane carbon skeleton, the absolute configuration of compound 5 was established as 3S,4R,7S,8S,11R,12S,13R by application of vibrational circular dichroism (VCD). In vitro anti-TB screenings revealed that metabolites 2–4 and, in particular, semisynthetic analogue 5, are strong growth inhibitors of Mycobacterium tuberculosis H37Rv.

Description: Chemicals targeting the liver stage (LS) of the malaria parasite are useful for causal prophylaxis of malaria. In this study, four lichen metabolites, evernic acid (1); vulpic acid (2), psoromic acid (3), and, (+)-usnic acid (4), were evaluated against LS parasites of Plasmodium berghei. Inhibition Of P. falciparum blood Stage (BS) parasites was also assessed to determine stage specificity. Compound 4 displayed the highest LS activity and stage specificity (LS IC50 value 2.3 mu M, BS IC50 value 47.3 mu M). The compounds 1 - 3 inhibited one Or more enzymes (Pf FabI, PfFabG, and pfFabZ), from the Plasmodial fatty acid biosynthesis (FAS-II) pathway, a potential drug. target for LS activity. To determine species specificity and to clarify the mechanism of reported antibacterial effects, 1-4 were also evaluated against FabI homologues and Whole cells of various pathogens -(S. aureus, E. coli M. tuberculosis). Molecular modeling studies suggest that lichen acids act indirectly via binding to allosteric sites on the protein surface of the FAS-II enzymes. Potential. toxicity, of compounds was assessed in human hepatocyte and cancer cells (in vitro) as well as in a zebrafish model (in vivo):. This study indicates the therapeutic and prophylactic potential of lichen metabolites as antibacterial and antiplasmodial agents.

Description: Analysis of maximum depth of occurrence of 11 952 marine fish species shows a global decrease in species number (N) with depth (x; m): log10 N = -0·000422x + 3·610000 (r(2)  = 0·948). The rate of decrease is close to global estimates for change in pelagic and benthic biomass with depth (-0·000430), indicating that species richness of fishes may be limited by food energy availability in the deep sea. The slopes for the Classes Myxini (-0·000488) and Actinopterygii (-0·000413) follow this trend but Chondrichthyes decrease more rapidly (-0·000731) implying deficiency in ability to colonize the deep sea. Maximum depths attained are 2743, 4156 and 8370 m for Myxini, Chondrichthyes and Actinopterygii, respectively. Endemic species occur in abundance at 7-7800 m depth in hadal trenches but appear to be absent from the deepest parts of the oceans, 〉9000 m deep. There have been six global oceanic anoxic events (OAE) since the origin of the major fish taxa in the Devonian c. 400 million years ago (mya). Colonization of the deep sea has taken place largely since the most recent OAE in the Cretaceous 94 mya when the Atlantic Ocean opened up. Patterns of global oceanic circulation oxygenating the deep ocean basins became established coinciding with a period of teleost diversification and appearance of the Acanthopterygii. Within the Actinopterygii, there is a trend for greater invasion of the deep sea by the lower taxa in accordance with the Andriashev paradigm. Here, 31 deep-sea families of Actinopterygii were identified with mean maximum depth 〉1000 m and with 〉10 species. Those with most of their constituent species living shallower than 1000 m are proposed as invasive, with extinctions in the deep being continuously balanced by export of species from shallow seas. Specialized families with most species deeper than 1000 m are termed deep-sea endemics in this study; these appear to persist in the deep by virtue of global distribution enabling recovery from regional extinctions. Deep-sea invasive families such as Ophidiidae and Liparidae make the greatest contribution to fish fauna at depths 〉6000 m.

Description: New indicators for optical CO2 sensors are synthesized in two steps from the commercially available diketo-pyrrolo-pyrrole (DPP) pigments Irgazin Ruby and Irgazin Scarlet. After introduction of bis(2-ethylhexyl) sulfonamide groups via a simple two-step synthesis, the pigments are rendered highly soluble in organic solvents and in polymers and show pH-dependent absorption and emission spectra. The new indicators have molar absorption coefficients in a 20 000–50 000 M–1 cm–1 range, possess quantum yields close to unity, and feature good photostability. The indicators along with a quaternary ammonium base are embedded into ethyl cellulose to give optical carbon dioxide sensors. The absorption and emission spectra of the deprotonated form are bathochromically shifted by more than 100 nm compared to the neutral form (λmax absorption 496–550 nm; λmax emission 564–587 nm). This enables colorimetric read-out and self-referenced ratiometric fluorescence intensity measurements. Importantly, the dynamic range of the sensors based on the new indicators is significantly different (0–10 kPa and 1–100 kPa CO2) that enables a broad variety of applications. New DPP dyes are conveniently prepared from commercially available pigments and represent a new class of colorimetric and fluorescent pH indicators for optical carbon dioxide sensors.

Description: Undaria pinnatifida, commonly known as wakame in Japan, is one species of brown seaweeds containing valuable bioactive organic compounds such as fucoxanthin, a carotenoid, which has numerous functional properties. However, most of the seaweeds that do not meet strict quality standards are normally discarded as wastes or returned to the sea, a situation which is becoming an environmental concern. In this research, supercritical carbon dioxide (SCCO2) extraction was investigated for the isolation of fucoxanthin. SCCO2 extraction experiments were carried out at temperature range of 25–60 °C and pressure range of 20–40 MPa, at a carbon dioxide flow rate of 1.0–4.0 mL/min. Results showed that fucoxanthin recovery closed to 80% could be obtained at 40 °C and 40 MPa in extraction time of 180 min. The recovery increased with decreasing temperature and increasing pressure. Pretreatment with microwave (MW) also enhanced the efficiency of extraction due most likely to disruption of the cell membrane. Application of SCCO2, generally regarded as safe and environmentally benign solvent, for extraction of useful bioactive compounds from unwanted or substandard seaweeds look promising in the near future. The extracts obtained using the method can be utilized as food and pharmaceutical additive, and can be used in the development of new health supplements.

Description: A number of rapid climate oscillations occur during the Lateglacial–Early Holocene, 15–8 ka BP period and a well-developed tephrostratigraphy in association with these oscillations increases the possibilities to correlate climate archives around the North Atlantic. This paper presents a tephrostratigraphy for Fosen peninsula, Central Norway. Both the Vedde Ash ca.12.1 ka BP and the Saksunarvatn Ash ~10.3 ka BP are important isochrones for correlations of Late Quaternary palaeoenvironmental records in the North Atlantic region and have been assigned ages in GICC05. Beside these tephras we have also identified a new tephra, the Fosen Tephra, with a Borrobol-type geochemistry that occurs above both the Vedde Ash and the Saksunarvatn Ash with an age ~10.2 ka BP. Several tephras with Borrobol-type geochemistry have been identified around the North Atlantic. One group is the Borrobol/Penifiler tephras dated to Greenland Interstadial-1 and another group is dated to the Early Holocene. We suggest that some of the Early Holocene Borrobol-type tephras and the Fosen Tephra may actually be the same layer. If so, the Fosen Tephra is spread over a large area of the North Atlantic and has the potential to become an important marker for short-term climate variability in Scandinavia and in the northern hemisphere.

Description: Hundreds of Sepia officinalis were hatched and cultured through the life cycle in each of 13 populations. Two genetic lines were maintained: one for an unprecedented seven generations and another presently in its fourth. All generations—save one—produced animals in excess of 1·0 kg body weight. Seven of eight generations with adequate data records had mean weights of 1–2 kg, and the largest cuttlefish reared were a male 2·6 kg and a female 2·9 kg. Fecundity levels were high, but there was a trend towards decreased fertility in later generations, with fertilization rates dropping below 10%. In the 7th generation, most mature animals failed to engage in agonistic courtship and mating behaviour. Almost no normal eggs were laid and none was fertile, thus ending the lineage. Most culture took place at 20–24°C and temperature generally explained variations in life span duration: being of shorter length at higher temperatures. Life spans were consistently longer at 20°C and sizes were greater than predicted from previously published literature. In both lines there was a trend towards larger individuals and longer life spans in subsequent generations. Survival of hatchlings typically exceeded 90% for two months post-hatching, and survival averaged 50% or higher to sexual maturity when corrected for animals removed from the populations for experimental use.

Description: The round goby Neogobius melanostomus is one of the most wide-ranging invasive fish on earth, with substantial introduced populations within the Laurentian Great Lakes watershed, the Baltic Sea and several major European rivers. Rapid expansion and deleterious ecosystem effects have motivated extensive research on this species; here this research is synthesized. Maps of the global distribution are provided and the invasion history of N. melanostomus, which spread more rapidly at first in North America, but has undergone substantial expansion over the past decade in the Baltic Sea, is summarized. Meta-analyses comparing their size at age, diet, competitors and predators in North American and European ecosystems are provided. Size at age is region specific, with saline habitats typically supporting larger and faster growing individuals than fresh water. Neogobius melanostomus prey differs substantially between regions, demonstrating a capacity to adapt to locally abundant food sources. Neogobius melanostomus comprise at least 50% of the diet of eight taxa in at least one site or life stage; in total, 16 predator taxa are documented from the Laurentian Great Lakes v. five from Eurasia. Invasive N. melanostomus are the only common forage fish to heavily exploit mussels in the Laurentian Great Lakes and the Baltic Sea, facilitating the transfer of energy from mussels to higher trophic levels in both systems. Neogobius melanostomus morphology, life history, reproduction, habitat preferences, environmental tolerances, parasites, environmental effects, sampling strategies and management are also discussed. Neogobius melanostomus inhabit a wide range of temperate freshwater and brackish-water ecosystems and will probably continue to spread via ballast water, accidental bait release and natural dispersal worldwide. Climate change will probably enhance N. melanostomus expansion by elevating water temperatures closer to its energetic optimum of 26° C. Future research needs are presented; most pressing are evaluating the economic effects of N. melanostomus invasion, determining long-term population level effects of egg predation on game-fish recruitment and comparing several variables (density, ecological effects morphology and life history) among invaded ecosystems. This review provides a central reference as researchers continue studying N. melanostomus, often as examples for advancing basic ecology and invasion biology.

Description: The relative roles of temperature and food availability on the seasonal and daily growth of whitefish Coregonus lavaretus larvae were investigated in the oligotrophic peri-alpine Lake Annecy, France. During the spring from 2004 to 2007, surface water temperature and density of potential zooplankton prey were monitored, and 2688 larvae were caught and measured. In addition, the daily growth of 130 larvae was estimated retrospectively by investigating the microstructure of their otoliths. Temperature played the predominant role in controlling both seasonal and daily growth of early larvae. In contrast, the abundance of Mesocyclops leuckarti and larval density was only slightly correlated to larval growth, suggesting no food limitation nor strong interindividual competition over the study period. Overall, these findings run counter to concerns about potential food limitation, but sound a warning about the potential impact of climate change on fish ecology and fisheries management.

Description: Molybdenum concentration and δ98/95Mo values for NIST SRM 610 and 612 (solid glass), NIST SRM 3134 (lot 891307; liquid) and IAPSO seawater reference material are presented based on comparative measurements by MC-ICP-MS performed in laboratories at the Universities of Bern and Oxford. NIST SRM 3134 and NIST SRM 610 and 612 were found to have identical and homogeneous 98Mo/95Mo ratios at a test portion mass of 0.02 g. We suggest, therefore, that NIST SRM 3134 should be used as reference for the δ–Mo notation and to employ NIST SRM 610 or 612 as solid silicate secondary measurement standards, in the absence of an isotopically homogeneous solid geological reference material for Mo. The δ98/95MoJMC Bern composition (Johnson Matthey ICP standard solution, lot 602332B as reference) of NIST SRM 3134 was 0.25 ± 0.09‰ (2s). Based on five new values, we determined more precisely the mean open ocean δ98/95MoSRM 3134 value of 2.09 ± 0.07‰, which equals the value of δ98/95MoJMC Bern of 2.34 ± 0.07‰. We also refined the Mo concentration data for NIST SRM 610 to 412 ± 9 μg g−1 (2s) and NIST SRM 612 to 6.4 ± 0.7 μg g−1 by isotope dilution. We propose these concentration data as new working values, which allow for more accurate in situ Mo determination using laser ablation ICP-MS or SIMS.

Description: Process length variation of cysts of the dinoflagellate Protoceratium reticulatum (Claparède et Lachmann) Bütschli in surface sediments from the North Pacific was investigated. The average process length showed a significant inverse relation to annual seawater density: σt annual = −0.8674 × average process length + 1029.3 (R2 = 0.84), with a standard error of 0.78 kg m−3. A sediment trap study from Effingham Inlet in British Columbia revealed the same relationship between average process length and local seawater density variations. In the Baltic–Skagerrak region, the average process length variation was related significantly to annual seawater density: σt annual = 3.5457 × average process length − 993.28 (R2 = 0.86), with a standard error of 3.09 kg m−3. These calibrations cannot be reconciled, which accentuates the regional character of the calibrations. This can be related to variations in molecular data (small subunit, long subunit and internal transcribed spacer sequences), which show the presence of several genotypes and the occurrence of pseudo-cryptic speciation within this species.

Description: In experimental metacommunities with marine benthic microalgae, we tested whether heat stress changes effects of connectivity and habitat heterogeneity on metacommunity structure and functioning, by manipulating a simulated heat wave, dispersal frequency and a light intensity gradient. We found that all measures of mean local and regional diversity and community biomass significantly declined after the heat wave and showed no sign of recovery. Additionally, dispersal decreased diversity and increased dominance in both the heat stressed and control communities. Together the heat wave and high dispersal frequency induced a dominance shift by spreading a temperature tolerant but low yielding species from its source patches with low light intensity across the metacommunity, an effect that increased with time. Although different species became dominant at high dispersal frequency with and without the heat wave, the shift towards a temperature tolerant species was not sufficient to maintain total community biomass. Thus, short-term disturbance may cause longer-term loss of ecosystem function due to dominance shifts in the composition of communities. This study illustrates the importance of employing multispecies approaches when attempting to predict responses of communities to environmental changes.

Description: The microbial communities were analyzed from commercially available dried dairy nutraceutical products, including 4 brands of dried colostrum, 2 brands of dried whey, and 1 brand of nonfat dry milk. A culture‐dependent 16S rRNA sequencing approach was utilized to elucidate the identity of individual isolates recovered from each dried dairy product. Approximately 69% of all bacterial isolates were members the genus of Bacillus, while approximately 14% of all bacterial isolates were identified as members of the genus Pseudomonas. Members of the Kocuria, Microbacterium, and Enterococcus genera were identified as well.

Description: Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO2-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH4 hydrate and mixed structure II CH4–C2H6 and CH4–C3H8 hydrates to gaseous CO2 as well as the reverse reaction, i.e., the conversion of CO2-rich structure I hydrate into structure II mixed hydrate. In the case of CH4–C3H8 hydrates, a conversion in the presence of gaseous CO2 from a supposedly more stable structure II hydrate to a less stable structure I CO2-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Description: Teleost fish grow continuously throughout their lifespan, and this growth includes visual system components: eyes, optic nerves, and brain. As fish grow, the optic nerve lengthens and neural signals must travel increasing distances from the eye to the optic tectum along thousands of retinal ganglion cell (RGC) axons. Larger fish have better vision that enhances their ability to capture prey, but they are faced with the potential computational problem of changes in the relative timing of visual information arriving at the brain. Optic nerve conduction delays depend on RGC axon conduction velocities, and velocity is primarily determined by axon diameters. If axon diameters do not increase in proportion to body length, then absolute and relative conduction delays will vary with fish size. We have measured optic nerve lengths and axon diameter distributions in different sized zebrafish (Danio rerio) and goldfish (Carassius auratus) and find that, as both species of fish grow, axon diameters increase to reduce average conduction delays by about half and to keep relative delays constant. This invariance of relative conduction delays simplifies computational problems faced by the optic tectum.

Description: As sessile filter feeders, sponges rely on a highly efficient fluid transport system. Their physiology depends on efficient water exchange, which is performed by the aquiferous system. This prominent poriferan anatomical character represents a dense network of incurrent and excurrent canals on which we lack detailed 3D models. To overcome this, we investigated the complex leucon‐type architecture in the demosponge Tethya wilhelma using corrosion casting, microtomography, and 3D reconstructions. Our integrative qualitative and quantitative approach allowed us to create, for the first time, high‐resolution 3D representations of entire canal systems which were used for detailed geometric and morphometric measurements. Canal diameters lack distinct size classes, and bifurcations are non‐uniformly ramified. A relatively high number of bifurcations show previously unknown and atypical cross‐sectional area ratios. Scaling properties and topological patterns of the canals indicate a more complex overall architecture than previously assumed. As a consequence, it might be more convenient to group canals into functional units rather than hierarchical clusters. Our data qualify the leucon canal system architecture of T. wilhelma as a highly efficient fluid transport system adapted toward minimal flow resistance. Our results and approach are relevant for a better understanding of sponge biology and cultivation techniques.

Description: The tephrostratigraphy of lake sediments in the Endinger Bruch provides the first robust age model for the Lateglacial palynological records of Vorpommern (north-east Germany). Cryptotephra investigations revealed six tephra layers within sediments spanning from Open vegetation phase I (∼Bølling, ∼15 ka) to the Early Holocene Betula/Pinus forest phase (∼Pre-boreal, ∼10.5 ka). Four of these layers have been correlated with previously described tephra layers found in sites across Europe. The Laacher See Tephra (Eifel Volcanic Field) is present in very high concentrations within sediments of the Lateglacial Betula (/Pinus) forest phase (∼Allerød). The Vedde Ash (Iceland) lies midway through Open vegetation phase III (∼Younger Dryas). The Hässeldalen and the Askja tephras (Iceland) lie in the Early Holocene Betula/Pinus forest phase (∼Preboreal). These tephra layers have independently derived age estimates, which have been imported into the Endinger Bruch record. Furthermore, the layers facilitate direct correlation of the regional vegetation record with other palaeoenvironmental archives, which contain one or more of the same tephra layers, from Greenland to Southern Europe. In doing this, localized variations are confirmed in some aspects of the pollen stratigraphy; however, transitions between the main vegetation phases appear to occur synchronously (within centennial errors) with the equivalent environmental transitions observed in sites across the European continent.

Description: Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg−1, it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm3 mol−1 from 0 to 50 °C. Volume properties of aqueous NaHSO4, NaOH, and NH3 have also been evaluated, at 25 °C only. In part 2 of this work (ref 1) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H2SO4 in 0−3 mol kg−1 aqueous solutions of the pure acid and to represent directly the effect of the HSO4− ↔ H+ + SO42− reaction. The results are incorporated into the treatment of aqueous H2SO4 density described here. Densities and apparent molar volumes from −20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

Description: Mussel aquaculture is a growing industry in Scotland, dominated by the production of Mytilus edulis. However, Mytilus trossulus, Mytilus galloprovincialis, and their hybrids with M. edulis have recently been detected in Scotland. At some farms, M. trossulus have been associated with significant losses in production because of presenting low meat yields and fragile shells. In the present study, M. edulis, M. trossulus, and their hybrids were examined from three cultivation areas in order to investigate shell and meat characteristics and advise on future management of mixed-species areas in Scotland. Results suggest that M. edulis is likely to consistently outperform M. trossulus and hybrids in mixed-species areas, but that M. trossulus meat yields from different areas can vary considerably. The ability to classify mussels into two (M. edulis and non-edulis) groups suggests that separation of M. trossulus genotypes could potentially be achieved by grading the harvested mussels. In the most affected areas, however, the fallowing of cultivation sites and importation of unispecific M. edulis spat appear as an alternative. Management of this problem in Scotland is likely to involve the implementation of area-specific measures, and the establishment of clear guidance on good practice aiming at preventing further distribution of M. trossulus.

Description: A total of 19 naturally occurring bromophenols, with six new and 13 known structures, were isolated and identified from the methanolic extract of the marine red alga Rhodomela confervoides. The new compounds were identified by spectroscopic methods as 3,4-dibromo-5-((methylsulfonyl)methyl)benzene-1,2-diol (1), 3,4-dibromo-5-((2,3-dihydroxypropoxy)methyl)benzene-1,2-diol (2), 5-(aminomethyl)-3,4-dibromobenzene-1,2-diol (3), 2-(2,3-dibromo-4,5-dihydroxyphenyl)acetic acid (4), 2-methoxy-3-bromo-5-hydroxymethylphenol (5), and (E)-4-(2-bromo-4,5-dihydroxyphenyl)but-3-en-2-one (6). Each compound was evaluated for free radical scavenging activity against DPPH (α,α-diphenyl-β-dipicrylhydrazyl) and ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt] radicals. Most of them exhibited potent activities stronger than or comparable to the positive controls butylated hydroxytoluene (BHT) and ascorbic acid. The results from this study suggest that R. confervoides is an excellent source of natural antioxidants, and inclusion of these antioxidant-rich algal components would likely help prevent the oxidative deterioration of food.

Description: We analyse the fluid flow regime within sediments on the Eastern levee of the modern Mississippi Canyon using 3D seismic data and downhole logging data acquired at Sites U1322 and U1324 during the 2005 Integrated Ocean Drilling Program (IODP) Expedition 308 in the Gulf of Mexico. Sulphate and methane concentrations in pore water show that sulphate–methane transition zone, at 74 and 94 m below seafloor, are amongst the deepest ever found in a sedimentary basin. This is in part due to a basinward fluid flow in a buried turbiditic channel (Blue Unit, 1000 mbsf), which separates sedimentary compartments located below and above this unit, preventing normal upward methane flux to the seafloor. Overpressure in the lower compartment leads to episodic and focused fluid migration through deep conduits that bypass the upper compartment, forming mud volcanoes at the seabed. This may also favour seawater circulation and we interpret the deep sulphate–methane transition zones as a result of high downward sulphate fluxes coming from seawater that are about 5–10 times above those measured in other basins. The results show that geochemical reactions within shallow sediments are dominated by seawater downwelling in the Mars-Ursa basin, compared to other basins in which the upward fluid flux is controlling methane-related reactions. This has implications for the occurrence of gas hydrates in the subsurface and is evidence of the active connection between buried sediments and the water column.

Description: This paper contains the results of an extensive isotopic study of United States Geological Survey GSD-1G and MPI-DING reference glasses. Thirteen different laboratories were involved using high-precision bulk (TIMS, MC-ICP-MS) and microanalytical (LA-MC-ICP-MS, LA-ICP-MS) techniques. Detailed studies were performed to demonstrate the large-scale and small-scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD-1G and the MPI-DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.

Description: Titanium (Ti) is present as a trace element in seawater at extremely low concentrations (5-350 pM, where 1 pM = 10(-12) mol L(-1)) throughout the water column. Presently, little is known about the marine biogeochemistry of Ti and there is a distinct lack of oceanic measurements of Ti, because of the combined difficulties of trace-metal clean sampling for an element at such low levels and the lack of a suitable shipboard method of analysis. Here, a new cathodic stripping voltammetry procedure is presented for the rapid determination of Ti at pM concentrations in seawater that is capable of being used directly at sea. This method utilizes the catalytic enhancement of the reduction of the complex formed between Cupferron (N-nitrosophenylhydroxylamine) and Ti(IV). While Cupferron itself acts as both a complexing agent and an oxidizing agent, it was found that the optimal sensitivity was with bromate as an auxiliary oxidant. An advantage of this method is that it is useable over the pH range of 5.5-8. Under the conditions employed in this work, detection limits ranged from 5 pM to 12 pM. This new catalytic method is significantly more sensitive than existing methods and has been extensively tested at sea in the Atlantic and Southern Oceans.