ALBERT

Description: Coccolithophores, a globally distributed group of marine phytoplankton, showed diverse responses to ocean acidification (OA) and to combinations of OA with other environmental factors. While their growth can be enhanced and calcification be hindered by OA under constant indoor light, fluctuation of solar radiation with ultraviolet irradiances might offset such effects. In this study, when a calcifying and a non-calcifying strain of Emiliania huxleyi were grown at 2 CO2 concentrations (low CO2 [LC]: 395 µatm; high CO2 [HC]: 1000 µatm) under different levels of incident solar radiation in the presence of ultraviolet radiation (UVR), HC and increased levels of solar radiation acted synergistically to enhance the growth in the calcifying strain but not in the non-calcifying strain. HC enhanced the particulate organic carbon (POC) and nitrogen (PON) productions in both strains, and this effect was more obvious at high levels of solar radiation. While HC decreased calcification at low solar radiation levels, it did not cause a significant effect at high levels of solar radiation, implying that a sufficient supply of light energy can offset the impact of OA on the calcifying strain. Our data suggest that increased light exposure, which is predicted to happen with shoaling of the upper mixing layer due to progressive warming, could counteract the impact of OA on coccolithophores distributed within this layer.

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: 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: In the 1930s the wasting disease pathogen Labyrinthula zosterae is believed to have killed 90% of the temperate seagrass Zostera marina in the Atlantic Ocean. Despite the devastating impact of this disease the host–pathogen interaction is still poorly understood, and few field studies have investigated factors correlating with the prevalence and abundance of L. zosterae. This study measures wasting disease in natural populations of Z. marina, showing a strong correlation between the disease and both salinity and water depth. No infection was detected in Z. marina shoots from low salinity (13–25 PSU) meadows, whereas most shoots carried the disease in high salinity (25–29 PSU). Shallow (1 m) living Z. marina shoots were also more infected compared to shoots in deeper (5 m) meadows. In addition, infection and transplantation experiments showed that Z. marina shoots from low salinity meadows with low pathogen pressure were more susceptible to L. zosterae infection. The higher susceptibility could not be explained by lower content of inhibitory defense compounds in the shoots. Instead, extracts from all Z. marina shoots significantly reduced pathogen growth, suggesting that Z. marina contains inhibitory compounds that function as a constitutive defense. Overall, the results show that seagrass wasting disease is common in natural Z. marina populations in the study area and that it increases with salinity and decreases with depth. Our findings also suggest that low salinity areas can act as a refuge against seagrass wasting disease.

Description: The high biodiversity of coral reefs results in complex trophic webs where energy and nutrients are transferred between species through a multitude of pathways. Here, we hypothesize that reef sponges convert the dissolved organic matter released by benthic primary producers (e.g. corals) into particulate detritus that is transferred to sponge-associated detritivores via the sponge loop pathway. To test this hypothesis, we conducted stable isotope (13C and15N) tracer experiments to investigate the uptake and transfer of coral-derived organic matter from the sponges Mycale fistulifera and Negombata magnifica to 2 types of detritivores commonly associated with sponges: ophiuroids (Ophiothrix savignyi and Ophiocoma scolopendrina) and polychaetes (Polydorella smurovi). Findings revealed that the organic matter naturally released by the corals was indeed readily assimilated by both sponges and rapidly released again as sponge detritus. This detritus was subsequently consumed by the detritivores, demonstrating transfer of coral-derived organic matter from sponges to their associated fauna and confirming all steps of the sponge loop. Thus, sponges provide a trophic link between corals and higher trophic levels, thereby acting as key players within reef food webs.

Description: Responses obtained in consonant perception experiments typically show a large variability across stimuli of the same phonetic identity. The present study investigated the influence of different potential sources of this response variability. It was distinguished between source-induced variability, referring to perceptual differences caused by acoustical differences in the speech tokens and/or the masking noise tokens, and receiver-related variability, referring to perceptual differences caused by within- and across-listener uncertainty. Consonant-vowel combinations consisting of 15 consonants followed by the vowel /i/ were spoken by two talkers and presented to eight normal-hearing listeners both in quiet and in white noise at six different signal-to-noise ratios. The obtained responses were analyzed with respect to the different sources of variability using a measure of the perceptual distance between responses. The speech-induced variability across and within talkers and the across-listener variability were substantial and of similar magnitude. The noise-induced variability, obtained with time-shifted realizations of the same random process, was smaller but significantly larger than the amount of within-listener variability, which represented the smallest effect. The results have implications for the design of consonant perception experiments and provide constraints for future models of consonant perception.

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: Nitrogen fixation is a key source of nitrogen in the Baltic Sea which counteracts nitrogen loss processes in the deep anoxic basins. Laboratory and field studies have indicated that single-strain nitrogen-fixing (diazotrophic) cyanobacteria from the Baltic Sea are sensitive to ocean acidification and warming, two drivers of marked future change in the marine environment. Here, we enclosed a natural plankton community in twelve indoor mesocosms (volume ~1400 L) and manipulated pCO2 to yield six CO2 treatments with two different temperature treatments (16.6°C and 22.4°C, pCO2 range = 360 – 2030 μatm). We followed the filamentous, heterocystous diazotrophic cyanobacteria community (Nostocales, primarily Nodularia spumigena) over four weeks. Our results indicate that heterocystous diazotrophic cyanobacteria may become less competitive in natural plankton communities under ocean acidification. Elevated CO2 had a negative impact on Nodularia sp. biomass, which was exacerbated by warming. Our results imply that Nodularia sp. may contribute less to new nitrogen inputs in the Baltic Sea in future.

Description: Nitrification, the step-wise oxidation of ammonium to nitrite and nitrate, is important in the marine environment because it produces nitrate, the most abundant marine dissolved inorganic nitrogen (DIN) component and N-source for phytoplankton and microbes. This study focused on the second step of nitrification, which is carried out by a distinct group of organisms, nitrite-oxidizing bacteria (NOB). The growth of NOB is characterized by nitrite oxidation kinetics, which we investigated for 4 pure cultures of marine NOB (Nitrospina watsonii 347, Nitrospira sp. Ecomares 2.1, Nitrococcus mobilis 231, and Nitrobacter sp. 311). We further compared the kinetics to those of non-marine species because substrate concentrations in marine environments are comparatively low, which likely influences kinetics and highlights the importance of this study. We also determined the isotope effect during nitrite oxidation of a pure culture of Nitrospina (Nitrospina watsonii 347) belonging to one of the most abundant marine NOB genera, and for a Nitrospira strain (Nitrospira sp. Ecomares 2.1). The enzyme kinetics of nitrite oxidation, described by Michaelis-Menten kinetics, of 4 marine genera are rather narrow and fall in the low end of half-saturation constant (Km) values reported so far, which span over 3 orders of magnitude between 9 and 〉1000 µM NO2-. Nitrospina has the lowest Km (19 µM NO2-), followed by Nitrobacter (28 µM NO2-), Nitrospira (54 µM NO2-), and Nitrococcus (120 µM NO2-). The isotope effects during nitrite oxidation by Nitrospina watsonii 347 and Nitrospira sp. Ecomares 2.1 were 9.7 ± 0.8 and 10.2 ± 0.9‰, respectively. This confirms the inverse isotope effect of NOB described in other studies; however, it is at the lower end of reported isotope effects. We speculate that differences in isotope effects reflect distinct nitrite oxidoreductase (NXR) enzyme orientations.

Description: Global climate change involves an increase in oceanic CO2 concentrations as well as thermal stratification of the water column, thereby reducing nutrient supply from deep to surface waters. Changes in inorganic carbon (C) or nitrogen (N) availability have been shown to affect marine primary production, yet little is known about their interactive effects. To test for these effects, we conducted continuous culture experiments under N limitation and exposed the bloomforming dinoflagellate species Scrippsiella trochoidea and Alexandrium fundyense (formerly A. tamarense) to CO2 partial pressures (pCO(2)) ranging between 250 and 1000 mu atm. Ratios of particulate organic carbon (POC) to organic nitrogen (PON) were elevated under N limitation, but also showed a decreasing trend with increasing pCO(2). PON production rates were highest and affinities for dissolved inorganic N were lowest under elevated pCO(2), and our data thus demonstrate a CO2-dependent trade-off in N assimilation. In A. fundyense, quotas of paralytic shellfish poisoning toxins were lowered under N limitation, but the offset to those obtained under N-replete conditions became smaller with increasing pCO(2). Consequently, cellular toxicity under N limitation was highest under elevated pCO(2). All in all, our observations imply reduced N stress under elevated pCO(2), which we attribute to a reallocation of energy from C to N assimilation as a consequence of lowered costs in C acquisition. Such interactive effects of ocean acidification and nutrient limitation may favor species with adjustable carbon concentrating mechanisms and have consequences for their competitive success in a future ocean.

Description: Previous bioassays conducted in the oligotrophic Atlantic Ocean identified availability of inorganic nitrogen (N) as the proximate limiting nutrient control of primary production, but additionally displayed a synergistic growth effect of combined N and phosphorus (P) addition. To classify conditions of nutrient limitation of coastal phytoplankton in the tropical ocean, we performed an 11 d nutrient-enrichment experiment with a natural phytoplankton community from shelf waters off northwest Africa in shipboard mesocosms. We used pigment and gene fingerprinting in combination with flow cytometry for classification and quantification of the taxon-specific photoautotrophic response to differences in nutrient supply. The developing primary bloom was dominated by diatoms and was significantly higher in the treatments receiving initial N addition. The combined supply of N and P did not induce a further increase in phytoplankton abundance compared to high N addition alone. A secondary bloom during the course of the experiment again displayed higher primary producer standing stock in the N-fertilized treatments. Bacterial abundance correlated positively with phytoplankton biomass. Dominance of the photoautotrophic assemblage by N-limited diatoms in conjunction with a probable absence of any P-limited phytoplankton species prevented an additive effect of combined N and P addition on total phytoplankton biomass. Furthermore, after nutrient exhaustion, dinitrogen (N-2)-fixing cyanobacteria succeeded the bloom-forming diatoms. Shelf waters in the tropical eastern Atlantic may thus support growth of diazotrophic cyanobacteria such as Trichodesmium sp. subsequent to upwelling pulses.

Description: The combined effects of warming and overwintering copepod densities on the spring succession of Baltic Sea plankton were investigated using indoor mesocosms. Three zooplankton (1.5, 4 and 10 copepods L-1) and two temperature levels called ∆0°C and ∆6°C (0°C and 6°C above the present day temperature scenario for Kiel Bight) were chosen. Both, the timing and the duration of the protozooplankton (PZP) bloom were significantly affected by temperature, but not by copepod density. In contrast, the bloom intensity of PZP was highly affected by the factors temperature and copepod density and its interaction. This suggests that at elevated temperature conditions PZP grows faster but, at the same time, are subject to higher top-down control by copepods. At low temperatures and low copepod densities, PZP in turn fully escaped from copepod predation. Further changes in the overwintering copepod densities resulted in a strong ciliate suppression of which small-sized ciliates (〈30 µm) were especially vulnerable to copepod predation while other PZP size classes remained unaffected. In conclusion, the results presented point at a pivotal regulating role of overwintering copepods under future warming condition. Further, warming was shown to cause a distinct match between phytoplankton and PZP thus strengthening trophic pathways through PZP. Our findings are discussed in the context of the ‘trophic link-sink’ debate by considering potential alterations in the flux of matter and energy up the food web.

Description: Snow crabs Chionoecetes opilio are quite productive at suitable temperatures, but can also be abundant in water cold enough to depress settlement of larvae, growth, and reproduction. In much of the northern Bering Sea, bottom water temperatures are below -1°C for most or all of the year. Crab pelagic larvae prefer to settle at temperatures above 0°C, so we found high densities of juveniles only where intruding warm currents deposited larvae in localized areas. After settlement, maturing crabs appeared to exhibit ontogenetic migration toward deeper, warmer water. Cold temperatures excluded key predators, but decreased fecundity by restricting females to small body size (with associated small clutches) and to breeding every 2 yr. Migration to warmer water may allow females to breed annually and to encounter more adult males needed to fertilize subsequent clutches. Because older males also emigrate, remaining adolescent males probably inseminate newly maturing females. Without localized intrusion of warmer currents, snow crabs might not persist at high densities in such cold waters. However, they are currently very abundant, and export many pelagic larvae and adults.

Description: Many ecosystems are facing biodiversity loss and environmental change due to anthropogenic activities, with these impacts occurring within the context of natural disturbance. Understanding ecosystem functioning and the response of communities to these impacts is necessary in order to evaluate the effects of future environmental change. The aim of this study was to determine the consequences of the loss of key species on the structure and function of intertidal communities in a context of nutrient enrichment, so as to ascertain the resistance of these communities when disturbance and stresses are compounded. Subarctic rocky intertidal communities in Quebec were subjected to an orthogonal factorial field experiment with 3 stress factors (macroalgae canopy loss, grazer exclusion, and nutrient enrichment), each with 2 disturbance levels. Simple and interactive effects of these factors were followed for 4 mo, and responses in structure (% cover and biomass) and productivity were evaluated. The communities that were not subjected to canopy loss showed greater resistance and very limited effects from enrichment and grazer reduction. The loss of canopy altered the community structure (e.g. reduction in richness and biomass) and functioning (reduced productivity), probably due to increased temperatures and desiccation. This lack of resistance was amplified through the addition of a stress. The application of multiple stresses within field experiments allows for a better understanding of the mechanisms affecting community structure and ecosystem functioning under situations of increased natural and anthropogenic stress.

Description: There is growing evidence that average global phytoplankton concentrations have been changing over the past century, yet published trajectories of change are highly divergent. Here, we review and analyze 115 published phytoplankton trend estimates originating from a wide variety of sampling instruments to explore the underlying patterns and ecological implications of phytoplankton change over the period of oceanographic measurement (1889 to 2010). We found that published estimates of phytoplankton change were much less variable when estimated over longer time series and consistent spatial scales and from the same sampling instruments. Average phytoplankton concentrations tended to increase over time in near-shore waters and over more recent time periods and declined in the open oceans and over longer time periods. Most published evidence suggests changes in temperature and nutrient supply rates as leading causes of these phytoplankton trends. In near-shore waters, altered coastal runoff and increased nutrient flux from land may primarily explain widespread increases in phytoplankton there. Conversely, in the open oceans, increasing surface temperatures are strengthening water column stratification, reducing nutrient flux from deeper waters and negatively influencing phytoplankton. Phytoplankton change is further affected by biological processes, such as changes in grazing regimes and nutrient cycling, but these effects are less well studied at large scales. The possible ecosystem consequences of observed phytoplankton changes include altered species composition and abundance across multiple trophic levels, effects on fisheries yield, and changing patterns of export production. We conclude that there is evidence for substantial changes in phytoplankton concentration over the past century, but the magnitude of these changes remains uncertain at a global scale; standardized long-term measurements of phytoplankton abundance over time can substantially reduce this uncertainty

Description: Benthic infauna in marine sediments have well-documented effects on biogeochemical cycling, from individual to ecosystem scales, including stimulation of nitrification and nitrogen removal via denitrification. However, the effects of burrowing depth and irrigation patterns on nitrogen cycling have not been as well described. Here we examined the effects of lugworm behavior on sediment nitrogen cycling using a reaction-transport model parameterized with literature and laboratory data. Feeding pocket depth and pumping characteristics (flow rate and pattern) were varied, and rates of nitrification, denitrification, and benthic exchange fluxes were computed. As expected, more intense burrow irrigation stimulated denitrification and coupled nitrification-denitrification. At high pumping rates and low sediment oxygen consumption rates (~10-6 mol m-3 s-1), simulation results showed a decrease in rates of nitrification and denitrification with decreasing burrow depth due to incomplete consumption of injected oxidants. Model results also suggest that discontinuous irrigation leads to temporal variability in sediment nitrogen cycling, but that the time-averaged rates do not depend on the irrigation pattern. We identify (1) the poorly constrained chemical composition of lumen fluid injected into sediments and (2) the response of microbial activity/distribution to oscillating redox conditions as critical knowledge gaps affecting estimates of sediment nitrogen removal.

Description: We applied a 2-step clustering algorithm and Bayesian stable isotope mixing model to examine intraspecific differences in the contribution of prey sources to the diet and foraging habitat of harbor seals Phoca vitulina in the Salish Sea, USA. We analyzed stable isotopes of carbon and nitrogen collected from 32 seals and 248 prey samples representing 18 of 25 of the most common seal prey items identified in seal scat. Stable isotope analyses identified significant harbor seal sex- and size-based differences in diet and foraging habitat use. In comparison to males, female harbor seals had a higher contribution of prey items that were more 13C-enriched. This result may indicate that females derived more of their δ13C value from nearshore versus offshore food webs, an explanation supported by movement data on this population. However, large seals of both sexes displayed a greater offshore signal in their diet, indicating that seal mass effects on foraging habitat use were somewhat independent of sex. Our work contributes to understanding trophic linkages between these generalist consumers and their prey. The foraging differences that we detected between male and female harbor seals present complex challenges for fisheries management and for the design of marine reserves. Many marine reserves in the Pacific Northwest are located in close proximity to seal haul-out sites. By lowering the energetic costs of foraging of females, these reserves may ultimately have the unintended effect of increasing individual fitness, population growth rate, and influencing future predator-induced mortality on endangered species.

Description: Within mono-specific meadows of clonal plants, genotypic diversity may functionally replace species diversity. Little is known about the variability in performance and plasticity of different genotypes towards anthropogenically induced stressors. In this field experiment we compared light-limitation stress responses and recovery of different eelgrass Zostera marina genotypes to assess the variability in phenotypic plasticity and gene expression between different genotypes. Replicated monoculture plots of 4 genotypes were subjected to a simulated turbidity period of 4 wk using shading screens, and their performance during light limitation and 4 wk of recovery was compared to non-shaded controls. In addition to growth and biomass, we investigated storage carbohydrates and quantified the expression of genes involved in carbohydrate metabolism, photosynthesis and control of oxidative stress. Plants showed remarkable plasticity in their stress responses and all phenotypic variables recovered to the control level within 4 wk. Depletion and subsequent restoration of sucrose levels differed among genotypes. In terms of gene expression, no consistent patterns were observed. Our study confirms that stress responses and recovery processes can vary substantially between genotypes and the results emphasize the importance of preserving regional genotypic diversity for immediate positive diversity effects and for adaptive evolution in response to global change.

Description: Heme is the iron-containing prosthetic group of hemoproteins, and is thus required for photosynthesis, respiration and nitrate reduction in marine phytoplankton. Here we report concentrations of heme b in Southern Ocean phytoplankton and contrast our findings with those in coastal species. The concentration of particulate heme b (pmol l-1) observed at the end of the exponential growth phase was related to the concentration of dissolved iron in the culture media. Small Southern Ocean phytoplankton species (〈6 μm in diameter) had heme b quotas 〈1 μmol mol-1 carbon, the lowest yet reported for marine phytoplankton. Heme b was also depleted in these species with respect to chlorophyll a. We calculated the amount of carbon accumulated per mole of heme b per second in our cultures (heme growth efficiency, HGE) and found that small Southern Ocean species can maintain growth rates, even while heme b content is reduced. Small Southern Ocean phytoplankton can thus produce more particulate carbon than larger Southern Ocean or small coastal species at equivalent iron concentrations. Combining primary productivity and heme b concentrations reported for the open ocean, we found that HGE in natural populations was within the range of our laboratory culture results. HGE was also observed to be higher at open ocean stations characterized by low iron concentrations. Our results suggest that low heme b quotas do not necessarily result in reduced growth and that marine phytoplankton can optimize iron use by manipulating the intracellular hemoprotein pool

Description: We investigated the impacts of predicted ocean acidification and future warming on the quantity and nutritional quality of a natural phytoplankton autumn bloom in a mesocosm experiment. Since the effects of CO2-enrichment and temperature have usually been studied independently, we were also interested in the interactive effects of both aspects of climate change. Therefore, we used a factorial design with 2 temperature and 2 acidification levels in a mesocosm experiment with a Baltic Sea phytoplankton community. Our results show a significant time-dependent influence of warming on phytoplankton carbon, chlorophyll a, and particulate organic carbon. Phytoplankton carbon, for instance, decreased by more than half with increasing temperature at bloom time. Additionally, elemental carbon to phosphorus ratios (C:P) increased significantly, by approximately 5 to 8%, due to warming. Impacts of CO2 or synergetic effects of warming and acidification could not be detected. We suggest that stronger grazing pressure induced by temperature was responsible for the significant decline in phytoplankton biomass. Our results suggest that the biological effects of warming on Baltic Sea phytoplankton are considerable and will likely have fundamental consequences for trophic transfer in the pelagic food web

Description: Sprat Sprattus sprattus larvae were used as model organisms to evaluate whether larval lipids reflect in situ feeding conditions and can thus identify match-mismatch situations. In detail, we determined larval lipid content, growth rates based on RNA:DNA ratios, and fatty acid (FA) composition during the spawning season in the Central Baltic Sea, and evaluated these in light of feeding, mortality and recruitment (which were determined in parallel within the project ‘GLOBEC Germany’). Based on the opposing trend of RNA:DNA and lipid content, as well as on previous observations, we hypothesized that lipid content and current feeding conditions are largely uncoupled in the early life stages of sprat due to reduced lipid anabolism. However, lipids still provide information in several ways: (1) segmented generalised linear models proved to be a suitable tool for identifying phases of lipid catabolism during development, with the slope reflecting size-specific environmental starvation pressure. This method detected a previously identified mismatch situation with suitable prey in the early spawning season, which increased mortality of larger larvae. (2) Estimated starvation resistance, a proxy that accounts for temperature- and size-dependent metabolism, reflected the likelihood of near future starvation of individual larvae. (3) Principal component analyses on FAs identified monthly differences in diet composition. Biomarkers indicated a dinoflagellate and/or microbial loop based carbon flux to the larvae. (4) Regression analyses revealed lower docosahexaenoic acid (DHA) levels in spring, but no obvious effect on growth. Food quality was generally high, and its impact on larval survival was less evident than that of prey size suitability.

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: 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: Multiple investigators often generate data from seabed images within a single image set to reduce the time burden, particularly with the large photographic surveys now available to ecological studies. These data (annotations) are known to vary as a result of differences in investigator opinion on specimen classification and of human factors such as fatigue and cognition. These variations are rarely recorded or quantified, nor are their impacts on derived ecological metrics (density, diversity, composition). We compared the annotations of 3 investigators of 73 megafaunal morphotypes in ~28 000 images, including 650 common images. Successful annotation was defined as both detecting and correctly classifying a specimen. Estimated specimen detection success was 77%, and classification success was 95%, giving an annotation success rate of 73%. Specimen detection success varied substantially by morphotype (12-100%). Variation in the detection of common taxa resulted in significant differences in apparent faunal density and community composition among investigators. Such bias has the potential to produce spurious ecological interpretations if not appropriately controlled or accounted for. We recommend that photographic studies document the use of multiple annotators and quantify potential inter-investigator bias. Randomisation of the sampling unit (photograph or video clip) is clearly critical to the effective removal of human annotation bias in multiple annotator studies (and indeed single annotator works).

Description: The Green's function (GF) for the scalar wave equation is numerically constructed by an advanced geometric ray-tracing method based on the eikonal approximation related to the semiclassical propagator. The underlying theory is first briefly introduced, and then it is applied to acoustics and implemented in a ray-tracing-type numerical simulation. The so constructed numerical method is systematically used to calculate the sound field in a rectangular (cuboid) room, yielding also the acoustic modes of the room. The simulated GF is rigorously compared to its analytic approximation. Good agreement is found, which proves the devised numerical approach potentially useful also for low frequency acoustic modeling, which is in practice not covered by geometrical methods.

Description: The community respiration of 2 tidally dominated cold-water coral (CWC) sites was estimated using the non-invasive eddy correlation (EC) technique. The first site, Mingulay Reef Complex, was a rock ridge located in the Sea of Hebrides off Scotland at a depth of 128 m and the second site, Stjernsund, was a channel-like sound in Northern Norway at a depth of 220 m. Both sites were characterized by the presence of live mounds of the reef framework-forming scleractinian Lophelia pertusa and reef-associated fauna such as sponges, crustaceans and other corals. The measured O2 uptake at the 2 sites varied between 5 and 46 mmol m–2 d–1, mainly depending on the ambient flow characteristics. The average uptake rate estimated from the ~24 h long deployments amounted to 27.8 ± 2.3 mmol m–2 d–1 at Mingulay and 24.8 ± 2.6 mmol m–2 d–1 at Stjernsund (mean ± SE). These rates are 4 to 5 times higher than the global mean for soft sediment communities at comparable depths. The measurements document the importance of CWC communities for local and regional carbon cycling and demonstrate that the EC technique is a valuable tool for assessing rates of benthic O2 uptake in such complex and dynamic settings.

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: 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 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: 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: 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: High-resolution 3D (HR3D) seismic data are important for hydrocarbon exploration of shallow reservoirs, site characterization, and geohazard assessments. The goal of this contribution is to identify and quantify the parameters to increase the resolution of HR3D seismic data to meter scale. The main acquisition parameters controlling the resolution of the collected data are the spectrum of the seismic source, source-receiver offset range, and trace density. An evolution to one-meter-scale resolution of 3D seismic will rely on combining a reproducible seismic source with high frequencies up to at least 600 Hz, a high uniform trace density of more than 4 million traces per square kilometer, and an offset range shorter than approximately 200 m. The resulting 3D seismic data volume will reach meter-scale resolution for water and target depths of less than 600 m. The proposed HR3D system will be suitable for 3D and 4D characterization of seabed properties and shallow stratigraphy, the identification of geohazards and hydrocarbon leakage, and monitoring the environmental impact of offshore activities. The P-Cable 3D system is an excellent starting point for achieving one-meter-scale resolution due to its flexible and tight meter-scale shot and receiver spacing.

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: Understanding mechanical interactions between hydrate and hosting sediments is critical for evaluating formation stability and associated environmental impacts of hydrate-bearing sediments during gas production. While core-scale studies of hydrate-bearing sediments are readily available and some explanations of observed results rely on pore-scale behavior of hydrate, actual pore-scale observations supporting the larger-scale phenomena are rarely available for hydrate-bearing sediments, especially with methane as guest molecules. The primary reasons for the scarcity include the challenge of developing tools for small-scale testing apparatus and pore-scale visualization capability. We present a testing assembly that combines pore-scale visualization and triaxial test capability of methane hydrate-bearing sediments. This testing assembly allows temperature regulation and independent control of four pressures: influent and effluent pore pressure, confining pressure, and axial pressure. Axial and lateral effective stresses can be applied independently to a 9.5 mm diameter and 19 mm long specimen while the pore pressure and temperature are controlled to maintain the stability of methane hydrate. The testing assembly also includes an X-ray transparent beryllium core holder so that 3D computed tomography scanning can be conducted during the triaxial loading. This testing assembly permits pore-scale exploration of hydrate-sediment interaction in addition to the traditional stress-strain relationship. Exemplary outcomes are presented to demonstrate applications of the testing assembly on geomechanical property estimations of methane-hydrate bearing sediments.

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: 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: 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: 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: Rising ocean temperature is expected to change the balance between production and degradation of organic matter due to different temperature sensitivities of auto- and heterotrophic processes. Copepods are the most prominent zooplankton group, and elevated temperature increases their growth and grazing rates. So far, it is unknown to what extent copepods affect the partitioning and stoichiometry of organic matter in a warmer surface ocean. We therefore conducted a mesocosm experiment with 3 copepod densities and 2 temperature scenarios to determine effects on the pools of dissolved and particulate organic matter and their C:N:P ratios. Here we show that particulate organic C (POC) concentrations decreased with increasing copepod abundance. This effect was more pronounced at elevated temperature, yielding a decrease in the POC to particulate nitrogen ratio (POC:PN) from 26 to 13 and in the POC:particulate organic phosphorus (POP) ratio from 567 to 257, from low to high copepod density. Dissolved organic carbon (DOC) accumulation was positively affected by temperature. However, increasing copepod abundance decreased the accumulation of DOC at elevated temperature. Copepod grazing and egestion enhanced the recycling of N and P, thereby increasing the availability of these nutrients for autotrophs. In concert with temperature-induced shifts in the phytoplankton community composition and size, changes in copepod abundance may therefore have contributed to altering the elemental composition of seston. Our findings suggest combined effects of zooplankton grazing and temperature on the composition and recycling of organic matter that should be taken into account when simulating biogeochemical cycles in a future ocean.

Description: Soft corals of the family Xeniidae are particularly abundant in Red Sea coral reefs. Their success may be partly due to a strong defense mechanism against fish predation. To test this, we conducted field and aquarium experiments in which we assessed the antifeeding effect of secondary metabolites of 2 common xeniid species, Ovabunda crenata and Heteroxenia ghardaqensis. In the field experiment, the metabolites of both investigated species reduced feeding on experimental food pellets in the natural population of Red Sea reef fishes by 86 and 92% for O. crenata and H. ghardaqensis, respectively. In the aquarium experiment, natural concentration of crude extract reduced feeding on experimental food pellets in the common reef fish Thalassoma lunare (moon wrasse) by 83 and 85%, respectively. Moon wrasse feeding was even reduced at extract concentrations as low as 12.5% of the natural concentration in living soft coral tissues. To assess the potential of a structural anti-feeding defence, sclerites of O. crenata were extracted and mixed into food pellets at natural, doubled and reduced concentration without and in combination with crude extract at 25% of natural concentration, and tested in an aquarium experiment. The sclerites did not show any effect on the feeding behavior of the moon wrasse indicating that sclerites provide structural support rather than antifeeding defense. H. ghardaqensis lacks sclerites. We conclude that the conspicuous abundance of xeniid soft coral species in the Red Sea is likely a consequence of a strong chemical defence, rather than physical defences, against potential predators.

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: 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: Recent studies on the life history of cephalopods have challenged the paradigm that all coleoid cephalopods have a single reproductive cycle and a short lifespan. Although lifespan has been investigated in several octopod species, few studies have considered their life-history traits in relation to environmental conditions via a comparative approach. We tested the hypothesis that octopod lifespan is correlated with habitat characteristics. For that purpose, life history and environmental data of 25 incirrate octopod species and the vampire squid Vampyroteuthis infernalis were compiled from the literature. Regression analysis showed that the relationship between age at maturity and average habitat temperature was best described by a negative power function (r2 = 0.86). The depth ranges of occurrence (minimum-midpoint-maximum) were positively correlated with time to reach maturity, with maximum depth showing the best fit (r2 = 0.47). Using literature data and our analyses, we estimated that octopods living in polar and deep seas mature after 3 to 5 yr. The reviewed and estimated instantaneous relative growth rates ranged from 0.1% body weight (BW) d-1 in the Antarctic species Pareledone charcoti to nearly 6% BW d-1 in the temperate species Macroctopus maorum. Our analyses suggest that low water temperatures (〈5°C) result in an extended ontogenetic development, potentially as a result of reduced metabolic rates and constraints on protein synthesis, which increases the lifespan of octopods living in cold environments.

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: In fisheries, vulnerability assessments - also commonly known as ecological risk assessments (ERAs) -have been an increasingly popular alternative to stock assessments to evaluate the vulnerability of non-target species in resource- and data-limited settings. The widely-used productivity-susceptibility analysis (PSA) requires detailed species-specific biological information and fishery susceptibility for a large number of parameters to produce a relative vulnerability score. The two major disadvantages of PSA are that each species is assessed against an arbitrary reference point, and PSA cannot quantify cumulative impacts of multiple fisheries. This paper introduces an Ecological Assessment of the Sustainable Impacts of Fisheries (EASI-Fish), a flexible approach that quantifies the cumulative impacts of fisheries on data-limited bycatch species, demonstrated in eastern Pacific Ocean (EPO) tuna fisheries. The method first estimates fishing mortality (F) based on the 'volumetric overlap' of each fishery with the distribution of each species. F is then used in length-structured per-recruit models to assess population vulnerability status using conventional biological reference points. Model results were validated by comparison with stock assessments for bigeye and yellowfin tunas in the EPO for 2016. Application of the model to 24 species of epipelagic and mesopelagic teleosts, sharks, rays, sea turtles and cetaceans and identification of the most vulnerable species is demonstrated. With increasing demands on fisheries to demonstrate ecological sustainability, EASI-Fish allows fishery managers to more confidently identify vulnerable species to which resources can be directed to either implement mitigation measures or collect further data for more formal stock assessment.

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: Oxygen (O2) deficiency and nutrient concentrations in marine systems are impacting organisms from microbes to higher trophic levels. In coastal and enclosed seas, O2 deficiency is often related to eutrophication and high degradation rates of organic matter. To investigate the impact of O2 concentration on bacterial growth and the turnover of organic matter, we conducted multifactorial batch experiments with natural microbial communities of the central Baltic Sea. Water was collected from suboxic (〈5 µmol L -1) depths in the Gotland Basin during June 2015. Samples were kept for four days under fully oxygenated and low O2 conditions (mean: 34 µmol L-1 O2), with or without nutrient (ammonium, phosphate, nitrate) and labile carbon (glucose) amendments. We measured bacterial abundance, bacterial heterotrophic production, extracellular enzyme rates (leucine-aminopeptidase) and changes in dissolved and particulate organic carbon concentrations. Our results show that the bacterial turnover of organic matter was limited by nutrients under both oxic and low O2 conditions. In nutrient and glucose replete treatments, low O2 concentrations significantly reduced the net uptake of dissolved organic carbon and lead to higher accumulation of more labile dissolved organic matter. Our results therewith suggest that the combined effects of eutrophication and deoxygenation on heterotrophic bacterial activity may potentially favor the accumulation of dissolved organic carbon in the Baltic Sea.

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 nature of many microbe-host interactions is not static, but may shift along a continuum from mutualistic to harmful depending on the environmental conditions. In this study, we assessed the interaction between the foundation plant eelgrass Zostera marina and the frequently associated protist Labyrinthula zosterae. We tested how an important environmental factor, nutrient availability, would modulate their interaction. We experimentally infected naive eelgrass plants in combination with 2 nutrient levels (fertilized and non-fertilized). We followed L. zosterae infection, eelgrass growth parameters and host defense gene expression over 3 wk in large 600 l tanks. Inoculation with L. zosterae and nutrient limitation both reduced eelgrass growth. These effects were additive, whereas no interaction of nutrient treatment and L. zosterae inoculation was detected. Gene expression levels of 15 candidate genes revealed a reduced expression of photosynthesis-related genes but an increased expression of classical stress genes such as Hsp80 in inoculated plants 2 d post-inoculation. However, we found no effects on plant mortality, and plants were able to clear high infection levels within 3 wk to ambient background levels of infection as assessed via specific RT-qPCR designed to quantify endophytic L. zosterae. Thus, we found no evidence that L. zosterae is a facultative mutualist that facilitates eelgrass growth under nutrient-limiting conditions. We suggest that the interaction between contemporary L. zosterae genotypes and Z. marina represents a mild form of parasitism in northern Europe because the damage to the plant is moderate even under nutrient limitation stress.

Description: In the northern hemisphere, eelgrass Zostera marina L. is the most important and widespread seagrass species. Despite its ecological importance, baseline data on eelgrass distribution and abundance are mostly absent, particularly in subtidal areas with relatively turbid waters. Here, we report a combined approach of vegetation mapping in the Baltic Sea coupled to a species distribution model (SDM). Eelgrass cover was mapped continuously in the summers of 2010 and 2011 with an underwater towed camera along ~400 km of seafloor. Eelgrass populated 80% of the study region and occurred at water depths between 0.6 and 7.6 m at sheltered to moderately exposed coasts. Mean patch length was 128.6 m but was higher at sheltered locations, with a maximum of 〉2000 m. The video observations (n = 7824) were used as empiric input to the SDMs. Using generalized additive models, 3 predictor variables (depth, wave exposure, and slope), which were selected based on Akaike’s information criterion, were sufficient to predict eelgrass presence/absence. Along with a very good overall discriminative ability (area under the receiver-operating characteristic curve ROC/AUC = 0.82), depth (as a proxy for light), wave exposure, and slope contributed 66, 29, and 5%, respectively, to the final model. The estimated total areal extent of eelgrass in the study region amounts to 140.5 km2 and comprises about 11.5% of all known Baltic seagrass beds. The present work is, to the best of our knowledge, the largest study undertaken to date on vegetation mapping and the first to assess distribution of eelgrass quantitatively in the western Baltic Sea.

Description: Brown skuas Catharacta antarctica lonnbergi breed across a broad latitudinal range from the Antarctic to temperate regions. While information on the non-breeding distribution and behaviour for Antarctic and subantarctic populations is known, no data exist for populations breeding at temperate latitudes. We combined geolocation sensing and stable isotope analysis of feather tissue to study the non-breeding behaviour of brown skuas from the temperate Chatham Islands, a population that was historically thought to be resident year-round. Analysis of 27 non-breeding tracks across 2 winters revealed that skuas left the colony for a mean duration of 146 d, which is 64% of the duration reported for Antarctic and subantarctic populations from King George Island, South Shetland Islands, and Bird Island, South Georgia. Consistent with populations of brown skuas from Antarctica and the Subantarctic, the distribution was throughout mixed subtropical-subantarctic and shelf waters. Stable isotope analysis of 72 feathers suggests that moulting takes place over mixed subtropical-subantarctic and subtropical shelf waters. We conclude that brown skuas from the Chatham Islands are migratory, but the year-round mild environmental conditions may reduce the necessity to leave their territories for extended periods.