ALBERT

Description: Non-technical summary Scenarios compatible with the Paris agreement's temperature goal of 1.5 °C involve carbon dioxide removal measures - measures that actively remove CO2 from the atmosphere - on a massive scale. Such large-scale implementations raise significant ethical problems. Van Vuuren et al. (2018), as well as the current IPCC scenarios, show that reduction in energy and or food demand could reduce the need for such activities. There is some reluctance to discuss such societal changes. However, we argue that policy measures enabling societal changes are not necessarily ethically problematic. Therefore, they should be discussed alongside techno-optimistic approaches in any kind of discussions about how to respond to climate change. Technical summary The 1.5 °C goal has given impetus to carbon dioxide removal (CDR) measures, such as bioenergy combined with carbon capture and storage, or afforestation. However, land-based CDR options compete with food production and biodiversity protection. Van Vuuren et al. (2018) looked at alternative pathways including lifestyle changes, low-population projections, or non-CO2 greenhouse gas mitigation, to reach the 1.5 °C temperature objective. Underlined by the recently published IPCC AR6 WGIII report, they show that demand-side management measures are likely to reduce the need for CDR. Yet, policy measures entailed in these scenarios could be associated with ethical problems themselves. In this paper, we therefore investigate ethical implications of four alternative pathways as proposed by Van Vuuren et al. (2018). We find that emission reduction options such as lifestyle changes and reducing population, which are typically perceived as ethically problematic, might be less so on further inspection. In contrast, options associated with less societal transformation and more techno-optimistic approaches turn out to be in need of further scrutiny. The vast majority of emission reduction options considered are not intrinsically ethically problematic; rather everything rests on the precise implementation. Explicitly addressing ethical considerations when developing, advancing, and using integrated assessment scenarios could reignite debates about previously overlooked topics and thereby support necessary societal discourse. Social media summary Policy measures enabling societal changes are not necessarily as ethically problematic as commonly presumed and reduce the need for large-scale CDR

Description: The Falkland Shelf is a highly productive ecosystem in the Southwest Atlantic Ocean. It is characterized by upwelling oceanographic dynamics and displays a wasp-waist structure, with few intermediate trophic-level species and many top predators that migrate on the shelf for feeding. One of these resident intermediate trophic-level species, the Patagonian longfin-squid Doryteuthis gahi, is abundant and plays an important role in the ecosystem. We used two methods to estimate the trophic structure of the Falkland Shelf food web, focusing on the trophic niche of D. gahi and its impacts on other species and functional groups to highlight the importance of D. gahi in the ecosystem. First, stable isotope measurements served to calculate trophic levels based on an established nitrogen baseline. Second, an Ecopath model was built to corroborate trophic levels derived from stable isotopes and inform about trophic interactions of D. gahi with other functional groups. The results of both methods placed D. gahi in the centre of the ecosystem with a trophic level of ∼ 3. The Ecopath model predicted high impacts and therefore a high keystoneness for both seasonal cohorts of D. gahi. Our results show that the Falkland Shelf is not only controlled by species feeding at the top and the bottom of the trophic chain. The importance of species feeding at the third trophic level (e.g. D. gahi and Patagonotothen ramsayi) and observed architecture of energy flows confirm the ecosystem's wasp-waist structure with middle-out control mechanisms at play.

Description: Increases in ocean temperatures in the Filchner Ronne region of Antarctica are likely to result in increased ice mass loss and sea level rise. We constrain projections of the 21st century sea level contribution of this region using process-based ice-sheet modeling, with model parameters controlling ice dynamics calibrated using observed surface speeds and Markov-chain Monte Carlo sampling. We use climate forcing from Representative Concentration Pathway (RCP) scenarios as well as a set of hypothetical scenarios of deep ocean warming to evaluate the sensitivity of this region to ocean temperatures. Projected changes in regional ice mass correspond to a decrease in global mean sea level of 24±7 mm over 2015–2100 under RCP 2.6 and 28±9 mm under RCP 8.5. Increased regional inland surface accumulation related to higher warming levels in RCP 8.5 leads to more ice above flotation, offsetting increased ice shelf basal melt. The tests involving step changes in ocean temperatures with constant surface forcing show that one degree of ocean warming from present results in an additional +11 mm contribution to sea level by 2100 and 1% of the ice-covered area in the domain becomes ungrounded (23 200 km2). The rate of mass loss with temperature increases at higher temperatures.

Description: Radiocarbon (14C) concentrations in the oceans are different from those in the atmosphere. Understanding these ocean-atmospheric 14C differences is important both to estimate the calendar ages of samples which obtained their 14C in the marine environment, and to investigate the carbon cycle. The Marine20 radiocarbon age calibration curve is created to address these dual aims by providing a global-scale surface ocean record of radiocarbon from 55,000–0 cal yr BP that accounts for the smoothed response of the ocean to variations in atmospheric 14C production rates and factors out the effect of known changes in global-scale palaeoclimatic variables. The curve also serves as a baseline to study regional oceanic 14C variation. Marine20 offers substantial improvements over the previous Marine13 curve. In response to community questions, we provide a short intuitive guide, intended for the lay-reader, on the construction and use of the Marine20 calibration curve. We describe the choices behind the making of Marine20, as well as the similarities and differences compared with the earlier Marine calibration curves. We also describe how to use the Marine20 curve for calibration and how to estimate ΔR—the localized variation in the oceanic 14C levels due to regional factors which are not incorporated in the global-scale Marine20 curve. To aid understanding, illustrative worked examples are provided.

Description: The Marine20 radiocarbon (14C) age calibration curve, and all earlier marine 14C calibration curves from the IntCal group, must be used extremely cautiously for the calibration of marine 14C samples from polar regions (outside ∼ 40ºS–40ºN) during glacial periods. Calibrating polar 14C marine samples from glacial periods against any Marine calibration curve (Marine20 or any earlier product) using an estimate of , the regional 14C depletion adjustment, that has been obtained from samples in the recent (non-glacial) past is likely to lead to bias and overconfidence in the calibrated age. We propose an approach to calibration that aims to address this by accounting for the possibility of additional, localized, glacial 14C depletion in polar oceans. We suggest, for a specific polar location, bounds on the value of during a glacial period. The lower bound may be based on 14C samples from the recent non-glacial (Holocene) past and corresponds to a low-depletion glacial scenario. The upper bound, , representing a high-depletion scenario is found by increasing according to the latitude of the 14C sample to be calibrated. The suggested increases to obtain are based upon simulations of the Hamburg Large Scale Geostrophic Ocean General Circulation Model (LSG OGCM). Calibrating against the Marine20 curve using the upper and lower bounds provide estimates of calibrated ages for glacial 14C samples in high- and low-depletion scenarios which should bracket the true calendar age of the sample. In some circumstances, users may be able to determine which depletion scenario is more appropriate using independent paleoclimatic or proxy evidence.

Description: Spatially variable basal conditions are thought to govern how ice sheets behave at glacial time scales (〉1000 years) and responsible for changes in dynamics between the core and peripheral regions of the Laurentide and Fennoscandian ice sheets. Basal motion is accomplished via the deformation of unconsolidated sediments, or via sliding of the ice over an undeformable bed. We present an ice sheet sliding module for the Parallel Ice Sheet Model (PISM) that takes into account changes in sediment cover and incorporates surface meltwater. This model routes meltwater, produced at the surface and base of the ice sheet, toward the margin of the ice sheet. Basal sliding is accomplished through the deformation of water saturated sediments, or sliding at the ice-bed interface. In areas with continuous, water saturated sediments, sliding is almost always accomplished through sediment deformation. In areas with incomplete cover, sliding has a stronger dependence on the supply of water. We find that the addition of surface meltwater to the base is a more important factor for ice sheet evolution than the style of sliding. In a glacial cycle simulation, our model causes a more rapid buildup of the Laurentide Ice Sheet.

Description: Although it is generally known that a combination of abiotic and biotic drivers shapes the distribution and abundance of parasites, our understanding of the interplay of these factors remains to be assessed for most marine host species. The present field survey investigated spatial patterns of richness, prevalence and abundance of parasites in Mytilus galloprovincialis along the coast of the northern Adriatic Sea. Herein, the relationships between biotic (host size, density and local parasite richness of mussel population) and abiotic (eutrophication and salinity) drivers and parasite richness of mussel individuals, prevalence and abundance were analysed. Local parasite richness was the most relevant factor driving parasite species richness in mussel individuals. Prevalence was mainly driven by eutrophication levels in 3 out of 4 parasite species analysed. Similarly, abundance was driven mainly by eutrophication in two parasite species. Mussel size, density and salinity had only minor contributions to the best fitting models. This study highlights that the influence of abiotic and biotic drivers on parasite infections in mussels can be differentially conveyed, depending on the infection measure applied, i.e., parasite richness, prevalence or abundance. Furthermore, it stresses the importance of eutrophication as a major factor influencing parasite prevalence and abundance in mussels in the Adriatic Sea

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: Trematode prevalence and abundance in hosts are known to be affected by biotic drivers as well as by abiotic drivers. In this study, we used the unique salinity gradient found in the south-western Baltic Sea to: (i) investigate patterns of trematode infections in the first intermediate host, the periwinkle Littorina littorea and in the downstream host, the mussel Mytilus edulis, along a regional salinity gradient (from 13 to 22) and (ii) evaluate the effects of first intermediate host (periwinkle) density, host size and salinity on trematode infections in mussels. Two species dominated the trematode community, Renicola roscovita and Himasthla elongata. Salinity, mussel size and density of infected periwinkles were significantly correlated with R. roscovita, and salinity and density correlated with H. elongata abundance. These results suggest that salinity, first intermediate host density and host size play an important role in determining infection levels in mussels, with salinity being the main major driver. Under expected global change scenarios, the predicted freshening of the Baltic Sea might lead to reduced trematode transmission, which may be further enhanced by a potential decrease in periwinkle density and mussel size.

Description: The last 85,000 years were characterized by high climate and environmental variability on the Yucatán Peninsula. Heinrich stadials are examples of abrupt climate transitions that involved shifts in regional temperatures and moisture availability. Thus, they serve as natural experiments to evaluate the contrasting responses of aquatic and terrestrial ecosystems. We used ostracodes and pollen preserved in a 75.9-m-long sediment core (PI-6, ~85 ka) recovered from Lake Petén Itzá, Guatemala, to assess the magnitude and velocity of community responses. Ostracodes are sensitive to changes in water temperature and conductivity. Vegetation responds to shifts in temperature and the ratio of evaporation to precipitation. Ostracodes display larger and more rapid community changes than does vegetation. Heinrich Stadial 5-1 (HS5-1) was cold and dry and is associated with lower ostracode and vegetation species richness and diversity. In contrast, the slightly warmer and dry conditions during HS6 and HS5a are reflected in higher ostracode species richness and diversity. Our paleoecological study revealed the greatest ecological turnover for ostracodes occurred from 62.5 to 51.0 ka; for pollen, it was at the Pleistocene/Holocene transition. Future studies should use various climate and environmental indicators from lake and marine sediment records to further explore late glacial paleoclimate causes and effects in the northern neotropics.

Description: Radiocarbon (14C) ages cannot provide absolutely dated chronologies for archaeological or paleoenvironmental studies directly but must be converted to calendar age equivalents using a calibration curve compensating for fluctuations in atmospheric 14C concentration. Although calibration curves are constructed from independently dated archives, they invariably require revision as new data become available and our understanding of the Earth system improves. In this volume the international 14C calibration curves for both the Northern and Southern Hemispheres, as well as for the ocean surface layer, have been updated to include a wealth of new data and extended to 55,000 cal BP. Based on tree rings, IntCal20 now extends as a fully atmospheric record to ca. 13,900 cal BP. For the older part of the timescale, IntCal20 comprises statistically integrated evidence from floating tree-ring chronologies, lacustrine and marine sediments, speleothems, and corals. We utilized improved evaluation of the timescales and location variable 14C offsets from the atmosphere (reservoir age, dead carbon fraction) for each dataset. New statistical methods have refined the structure of the calibration curves while maintaining a robust treatment of uncertainties in the 14C ages, the calendar ages and other corrections. The inclusion of modeled marine reservoir ages derived from a three-dimensional ocean circulation model has allowed us to apply more appropriate reservoir corrections to the marine 14C data rather than the previous use of constant regional offsets from the atmosphere. Here we provide an overview of the new and revised datasets and the associated methods used for the construction of the IntCal20 curve and explore potential regional offsets for tree-ring data. We discuss the main differences with respect to the previous calibration curve, IntCal13, and some of the implications for archaeology and geosciences ranging from the recent past to the time of the extinction of the Neanderthals.

Description: The concentration of radiocarbon (14C) differs between ocean and atmosphere. Radiocarbon determinations from samples which obtained their 14C in the marine environment therefore need a marine-specific calibration curve and cannot be calibrated directly against the atmospheric-based IntCal20 curve. This paper presents Marine20, an update to the internationally agreed marine radiocarbon age calibration curve that provides a non-polar global-average marine record of radiocarbon from 0–55 cal kBP and serves as a baseline for regional oceanic variation. Marine20 is intended for calibration of marine radiocarbon samples from non-polar regions; it is not suitable for calibration in polar regions where variability in sea ice extent, ocean upwelling and air-sea gas exchange may have caused larger changes to concentrations of marine radiocarbon. The Marine20 curve is based upon 500 simulations with an ocean/atmosphere/biosphere box-model of the global carbon cycle that has been forced by posterior realizations of our Northern Hemispheric atmospheric IntCal20 14C curve and reconstructed changes in CO2 obtained from ice core data. These forcings enable us to incorporate carbon cycle dynamics and temporal changes in the atmospheric 14C level. The box-model simulations of the global-average marine radiocarbon reservoir age are similar to those of a more complex three-dimensional ocean general circulation model. However, simplicity and speed of the box model allow us to use a Monte Carlo approach to rigorously propagate the uncertainty in both the historic concentration of atmospheric 14C and other key parameters of the carbon cycle through to our final Marine20 calibration curve. This robust propagation of uncertainty is fundamental to providing reliable precision for the radiocarbon age calibration of marine based samples. We make a first step towards deconvolving the contributions of different processes to the total uncertainty; discuss the main differences of Marine20 from the previous age calibration curve Marine13; and identify the limitations of our approach together with key areas for further work. The updated values for ΔR, the regional marine radiocarbon reservoir age corrections required to calibrate against Marine20, can be found at the data base http://calib.org/marine/.

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: In this Open Access book, Sander van der Leeuw examines how the modern world has been caught in a socioeconomic dynamic that has generated the conundrum of sustainability. Combining the methods of social science and complex systems science, he explores how western, developed nations have globalized their world view and how that view has led to the sustainability challenges we are now facing. Its central theme is the coevolution of cognition, demography, social organization, technology, and environmental impact. Beginning with the earliest human societies, van der Leeuw links the distant past with the present in order to demonstrate how the information and communications technology revolution is undermining many of the institutional pillars on which contemporary societies have been constructed. An original view of social evolution as the history of human information-processing, his book shows how the past offers insight into the present and can help us deal with the future.

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: A new carbon isotope record for two high-latitude sedimentary successions that span the Jurassic–Cretaceous boundary interval in the Sverdrup Basin of Arctic Canada is presented. This study, combined with other published Arctic data, shows a large negative isotopic excursion of organic carbon (δ13Corg) of 4‰ (V-PDB) and to a minimum of −30.7‰ in the probable middle Volgian Stage. This is followed by a return to less negative values of c. −27‰. A smaller positive excursion in the Valanginian Stage of c. 2‰, reaching maximum values of −24.6‰, is related to the Weissert Event. The Volgian isotopic trends are consistent with other high-latitude records but do not appear in δ13Ccarb records of Tethyan Tithonian strata. In the absence of any obvious definitive cause for the depleted δ13Corg anomaly, we suggest several possible contributing factors. The Sverdrup Basin and other Arctic areas may have experienced compositional evolution away from open-marine δ13C values during the Volgian Age due to low global or large-scale regional sea levels, and later become effectively coupled to global oceans by Valanginian time when sea level rose. A geologically sudden increase in volcanism may have caused the large negative δ13Corg values seen in the Arctic Volgian records but the lack of precise geochronological age control for the Jurassic–Cretaceous boundary precludes direct comparison with potentially coincident events, such as the Shatsky Rise. This study offers improved correlation constraints and a refined C-isotope curve for the Boreal region throughout latest Jurassic and earliest Cretaceous time.

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: 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: 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: 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: Recent rapid retreat of glacial front lines and the loss of land ice along the Antarctic margins may play an important role in exporting suspended particulate matter (SPM) potentially rich in bioavailable (defined as ascorbate leachable) iron (FeA) to coastal areas of the Southern Ocean. Sediment ablation is an additional source of iron for this high-nutrient low-chlorophyll region. In Potter Cove, King George Island, meltwater streams discharge up to 18 000 mg l-1 (average 283 mg l-1) of slightly weathered, finely ground bedrock particles into coastal waters during the summer. Approximately 15% of this SPM is exported within a low-salinity surface plume into Bransfield Strait. Based on our data, an estimated 12 mg m-2 yr-1 of FeA is exported from the South Shetland Island land surface (ice-free and subglacial areas) to the surrounding coastal waters. Extrapolated to an area of 2.5x104 km2, this FeA input is comparable to the contribution from icebergs and c. 240-fold higher than aeolian input via dust. An observed rise in local sediment accumulation rates suggests that glacial erosion has been increasing over recent decades and that (sub-)glacially derived SPM is becoming more important as a source of iron to the Southern Ocean.

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: 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: Since the Last Glacial Maximum, ice has retreated through the fjords of the South Shetland Islands leaving a valuable record of submarine landforms behind. In this study, glacial landforms and sub-bottom characteristics have been mapped to investigate the late Holocene retreat behaviour of the Fourcade Glacier and to delineate past environmental processes in Potter Cove, King George Island. The comprehensive datasets include high-resolution swath bathymetry, shallow seismic profiling and one sediment core. Moraines, moraine incisions and glacial lineations were mapped on the sea floor in the inner part of the cove, whereas pockmarks, ice scour marks and channel structures were identified in the outer part. Sub-bottom characteristics have been assigned to different acoustic facies types indicating different depositional settings. The results reveal glacial recessions as well as stillstands and potential readvances during the late Holocene. Furthermore, the sediment record indicates that the Fourcade Glacier was situated inside the inner cove during the Little Ice Age (500–100 cal yr bp).

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: Introduction. Today, most countries have accepted a 2 degrees Celsius temperature increase above preindustrial levels as the maximum tolerable limit for global warming. An exceedance probability of below 20 percent for this limit implies an emission budget of less than 250 GtC from 2000 until 2049, however, extrapolating from current global CO2 emissions, this budget will only last until 2024. This sobering math should wake us up to the reality that all options, including climate engineering, need to be considered to address climate change. Climate engineering options can be classified broadly into two categories: solar radiation management and carbon dioxide removal measures. Solar radiation management schemes seek to decrease the incoming solar radiation or to increase the reflection of incoming solar radiation. These approaches can generate fast climate responses, but do not immediately address the cause of the problem. Carbon dioxide removal measures seek to decrease atmospheric carbon concentrations by enhancing or substituting natural carbon sinks. The terrestrial carbon sink can be enhanced by means of forestation; the oceanic sink may, in some regions, be enhanced by means of fertilization, for example by artificially enhanced upwelling of macronutrients or by purposeful addition of the micronutrient iron; the mineral carbon sink can be enhanced by means of chemically accelerated weathering. Some analysts have expressed doubts about the potential of mitigating climate change by sink enhancement, because of concerns about whether carbon can be stored permanently. Nevertheless, terrestrial vegetation sinks have entered the Kyoto Protocol (KP) as offsets for anthropogenic greenhouse gas emissions, but ocean sinks have not.

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: Density distribution of the common infaunal bivalves, Macoma balthica and Cerastoderma edule, was studied along the Murman Coast of the Barents Sea during 2002–2010. In both species, abundance was generally higher in West Murman in contrast to East Murman. Highest density of Macoma balthica reaching 1535 ind. m−2 was observed in the Kola Inlet. Cerastoderma edule was less abundant; its density rarely exceeded 10 ind. m−2 in all but one site, where 282 ind. m−2 was registered. Reconstruction of abundance distribution across the European geographic range of Macoma balthica revealed that it does not match an ‘abundant-centre’ pattern, having features of ramped north. On the other hand, distribution of Cerastoderma edule abundance across the range generally follows an ‘abundant-centre’ pattern but southern edge populations show relatively higher abundances as compared with those at the north edge (the Barents Sea).

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: 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: 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: 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: No published information is available on the foraging ecology and choice of feeding habitat of New Zealand’s rarest breeding bird: the New Zealand Fairy Tern (NZFT) Sternula nereis davisae. To address this gap, we conducted an assessment of the largest remaining breeding population at Mangawhai Harbour, Northland, New Zealand, during the chick-rearing period of the 2010/2011 breeding season. We combined visual tracking of birds with prey surveys and stable isotope analyses, and we present the first quantitative assessment of NZFT foraging. We recorded 405 foraging dives that show NZFT foraging habitat includes the water edges, shallow channels, and pools on the tidal flats of mangrove-lined (Avicennia marina var. resinifera) parts of the estuary; tidal pools on mud- and sandflats in the mid-estuary and lower harbour; the shallow margins of the dredged main channel in the lower harbour; the oxbow lagoons on the sand spit; and coastal shallows. Our study identifies the mangrove-lined highly tidal and shallow mid-estuary and the lagoon on the sand spit as foraging hotspots for the Mangawhai breeding population of the NZFT. The prey survey employed a seine-net sampling method at identified NZFT foraging sites and yielded 4,367 prey-sized fish of 11 species, two of which had not previously been reported in Mangawhai Harbour, as well as numerous shrimps. The most abundant fish were gobies of the genus Favonigobius. Our stable isotope results highlight gobies as the most important prey for NZFT chick rearing, also indicating that flounder Rhombosolea sp. contribute to NZFT diet. We raise the possibility that shrimps may also constitute a substantial diet component for NZFT, potentially providing up to 21% of diet mass for adult birds. While our results provide a first basis to understanding the feeding ecology of NZFT during their breeding season in order to facilitate conservation planning, further research is required to address inter-annual variation and to identify key foraging grounds for this Critically Endangered bird at other breeding sites.

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: 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: 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: The feeding habits of the pelagic stingray ( Pteroplatytrygon violacea ) were studied using 84 stomachs of specimens caught in the northern Adriatic Sea in the period from April 2004 to October 2005. Percentage of empty stomachs found was overall very low, being a bit bigger in smaller specimens. The diet consisted of two main taxonomic groups such as teleost fish and cephalopods, but few specimens of crustaceans were recorded as well. The main food item was represented by anchovy, while cuttlefish and red band fish represented the alternative preys. Prey size was positively correlated with the size of predator. The proportion of anchovies in the diet grew with size of predator, while the one for red band fish decreased. The stingray was confirmed to be a top predator of pelagic fish species, although the presence of benthic prey shows that it feeds also at the bottom.

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: The schooling behaviour of the oval squid Sepioteuthis lessoniana was observed over 4 summers at 3 observation sites in the coastal waters of Okinawa Island, Ryukyu Archipelago, Japan. During this field study, 3 static appearances (belt, ball and sheet shape) and 2 transitional appearances (high and low density) were noted, recorded and described. In addition to formations, a member of S. lessoniana schools also displayed particular and repeated behavioural patterns such as vanguard and intimidating display. The 3 observation sites were tropical coral reefs near the coastline at a depth of 1 to 15 m on an average. All participating observers snorkelled and were equipped with various underwater digital video and photographic cameras. The schools observed consisted of 8 to over 100 members with a wide range of body sizes. Despite these biological and locational differences, both static and transitional appearances were consistently observed with equally consistent individual behavioural patterns. There have been studies on related species, Sepioteuthis sepioidea, at the San Blas Islands along the Caribbean coast of eastern Panama, and the same species, S. lessoniana, at a different geographical location, Casuarina Beach on Lizard Island, Australia. The findings of this study are consistent with those reported previously, with some notable differences.

Description: Age structure and hatchling dates of the squid Illex argentinus collected by bottom-trawl fishery in southern Brazilian waters were assessed by the analysis of statolith growth increments. Catches occurred between 2001 and 2002, from 23° to 32°S at depths of 100–700 m. Squid from juvenile to post-spawning stages were collected year round, with age estimated from 98 to 320 days and mantle lengths ranging from 112 to 376 mm. Duration of life cycle events based on statolith growth zones revealed that squids can spend about 14% of their lifespan as paralarva (~30 days), 70% as juvenile (~130 days), leaving maturity and spawning condition to the terminal 10–20% (~30–60 days). The results suggest that, unlike estimates available for Patagonian populations, a general 0.5 year lifespan is predicted for I. argentinus off Brazil. The wide range of size-at-ages implied that catches of shortfin squid off southern Brazil probably include squid hatched throughout the year. Mature and spawning squid caught in summer months hatched in winter and spring, while winter catches revealed mature-spawning individuals hatched both in summer/autumn (~6 months of age) and winter/spring periods (~10–11 months of age). It has been argued that such groups may combine both squid resident of Brazilian outer shelf and slope (22°–34°S) with a six months' lifespan and migrating squid originated from the northern Patagonian shelf (~42°S) with 10–11 months' lifespan.

Description: Intraspecific variation in characters such as arm sucker and gill lamellae counts in octopodids is yet to be thoroughly investigated, potentially hampering our ability to recognize species. In this study, data from 13 specimens of Muusoctopus hydrothermalis collected at four hydrothermal vents on the East Pacific Rise between 8°38′N and 12°48′N are considered. Although the northern and southern octopuses differ minimally in size, mean sucker count by arm in the northern group is 11.7 to 22.8% higher than it is in the southern group; in addition these octopuses typically have an additional gill lamella and bulkier funnel organs. The arms of each individual carry a different number of suckers. The difference is significant on nonadjacent arms, a pattern that merits examination in a broader taxonomic context. Why these differences exist among conspecifics remains unknown, the incidence of parasitic copepods is not different between the groups and the between-group variation in arm suckers seen here compares well with a previous report of variation among 18 specimens from the type locality. Increases in meristic characters (counts) in fish are attributed to lower temperatures during embryonic development following Jordan's rule. Northern and southern vents offer the octopuses a wide temperature range, but vent fluid chemistry differs. Northern vent fluids may be more toxic; if so, developing octopus embryos may survive only minimal vent fluid exposure and therefore develop at low temperatures. At the less toxic southern vents, eggs may survive greater exposure to vent fluids and thus develop at higher temperatures.

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: The Cycladic blueschist belt, Greece, is mostly submerged below sea level and regional correlations are difficult to establish. Marbles are widespread within the belt and locally used as marker horizons to subdivide monotonous schist sequences. However, owing to the lack of distinctive petrographic characteristics, the marbles have not been used for island-to-island correlations. This study aims to investigate the potential of Sr-, C- and O-isotope compositions of marbles as a tool for unravelling the litho- and/or tectonostratigraphic relationships across the Cycladic islands, and as a proxy for the time of sediment formation. For this purpose, we have studied metamorphic carbonate rocks from the islands of Tinos, Andros, Syros, Sifnos and Naxos. Identical 87Sr/86Sr values for certain marble horizons occurring on Tinos, Andros and Sifnos are interpreted to document coeval regional carbonate precipitation. The 87Sr/86Sr values of the apparently least altered samples intersect the seawater curve multiple times within the most likely time interval of original carbonate precipitation (〈 240 Ma; as indicated by previously published ion probe U–Pb zircon data) and thus an unequivocal age assignment is not possible. Very broad temporal correlations are possible, but more subtle distinctions are not feasible. On Andros, the overlapping Sr-isotope values of marbles representing the lowest and highest parts of the metamorphic succession are in accordance with a model suggesting isoclinal folding or thrusting of a single horizon, or very fast sedimentation. In contrast, distinct 87Sr/86Sr values for samples from Tinos, representing different levels of the metamorphic succession, suggest that these rocks represent a temporal succession and not the tectonic repetition of a single horizon. Based on Sr-,O- and C-isotope characteristics alone the time equivalence ofmarbles occurring on different islands could not be documented unambiguously. However, by using various combinations of these parameters, some occurrences can be discriminated from the overall sample population. The new data further accentuate the general potential of coupled Sr-, C- and O-isotope characteristics for identification of archaeological provenance and complement existing datasets for Aegean marbles.

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: 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: 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.

Description: The conversion of alkylboranes to the corresponding alkanes is classically per-formed via protonolysis of alkylboranes. This simple reaction requires the use of severe reaction conditions, that is, treatment with a carboxylic acid at high temperature (〉150 °C). We report here a mild radical procedure for the transformation of organoboranes to alkanes. 4-tert-Butylcatechol, a well-established radical inhibitor and antioxidant, is acting as a source of hydrogen atoms. An efficient chain reaction is observed due to the exceptional reactivity of phenoxyl radicals toward alkylboranes. The reaction has been applied to a wide range of organoboron derivatives such as B-alkylcatecholboranes, trialkylboranes, pinacolboronates, and alkylboronic acids. Furthermore, the so far elusive rate constants for the hydrogen transfer between secondary alkyl radical and catechol derivatives have been experimentally determined. Interestingly, they are less than 1 order of magnitude slower than that of tin hydride at 80 °C, making catechols particularly attractive for a wide range of transformations involving C−C bond formation.

Description: Macroalgae have for centuries been consumed whole among the East Asian populations of China, Korea, and Japan. Due to the environment in which they grow, macroalgae produce unique and interesting biologically active compounds. Protein can account for up to 47% of the dry weight of macroalgae depending on species and time of cultivation and harvest. Peptides derived from marcoalgae are proven to have hypotensive effects in the human circulatory system. Hypertension is one of the major, yet controllable, risk factors in cardiovascular disease (CVD). CVD is the main cause of death in Europe, accounting for over 4.3 million deaths each year. In the United States it affects one in three individuals. Hypotensive peptides derived from marine and other sources have already been incorporated into functional foods such as beverages and soups. The purpose of this review is to highlight the potential of heart health peptides from macroalgae and to discuss the feasibility of expanding the variety of foods these peptides may be used in.