Molecular dynamics simulations of the dipolar-induced formation of magnetic nanochains and nanorings

Iron, cobalt and nickel nanoparticles, grown in the gas phase, are known to arrange in chains and bracelet-like rings due to the long-range dipolar interaction between the ferromagnetic (or super-paramagnetic) particles. We investigate the dynamics and thermodynamics of such magnetic dipolar nanoparticles for low densities using molecular dynamics simulations and analyze the influence of temperature and external magnetic fields on two- and three-dimensional systems. The obtained phase diagrams can be understood by using simple energetic arguments.Comment: 6 pages, 6 figure

Sulfur isotope fractionation between fluid and andesitic melt : an experimental study

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 142 (2014): 501-521, doi:10.1016/j.gca.2014.07.015.Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55 to 7.95 wt% H2O, ~140 to 2700 ppm sulfur (S), and 0 to 1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030°C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz-fayalite-magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ~400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0 to 72 h (annealing time, tA) at the final P and quenched rapidly from 1030°C to room temperature (T). The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid-melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas-melt S isotope fractionation factor αg-m. No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ~0.9985 ± 0.0007 at >QFM+3 to ~1.0042 ± 0.0042 at ~QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34S g-m) in andesitic systems at 1030°C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope signatures in natural samples (e.g., melt inclusions or volcanic gases).This project was supported by the German Science Foundation (BE1720/25-1 to H. Behrens), by the German National Academic Foundation, and by Collaborative Research Grants from the U.S. National Science Foundation (EAR-0838482 to C. W. Mandeville, EAR-0838436 to N. Shimizu, and EAR- 0838328 to K. A. Kelley)

Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS)

Rinikerfeld Palaeolake (Northern Switzerland) – a sedimentary archive of landscape and climate change during the penultimate glacial cycle

While timing and ice extent of the last glacial maximum are generally well known, the courses of earlier glaciations have remained poorly constrained, with one of the main reasons being the scarcity of sedimentary archives. This study introduces a new palaeolake record from a Mid‐Pleistocene glaciofluvial channel system in the Lower Aare Valley (Northern Switzerland). The record of Rinikerfeld comprises a >40 m long succession of Quaternary deposits that are targeted by multi‐method sedimentological analysis. Sedimentary facies together with geochemical and geotechnical parameters, pollen content, as well as luminescence ages allow the reconstruction of the establishment, evolution and infilling of the early Marine Isotope Stage 6‐aged Rinikerfeld Palaeolake. A drastic change in lake sediment composition and structure indicates cessation of the initial glacially derived input, which is explained by landscape modification and drainage rerouting during the Penultimate (Beringen) Glaciation. Geochemical and palynological data further reveal cold, initially periglacial but slightly ameliorating, climate conditions, while the lake was progressively filled up by local runoff, before being buried by periglacial colluvial diamicts, and potentially overridden by ice. It is therefore concluded that the onset of the Beringen Glaciation was an environmentally as well as geomorphically dynamic time period in the Northern Alpine Foreland

Nitrogen deposition to the United States: distribution, sources, and processes

We simulate nitrogen deposition over the US in 2006–2008 by using the GEOS-Chem global chemical transport model at 1/2°×2/3° horizontal resolution over North America and adjacent oceans. US emissions of NO<sub>x</sub> and NH<sub>3</sub> in the model are 6.7 and 2.9 Tg N a<sup>−1</sup> respectively, including a 20% natural contribution for each. Ammonia emissions are a factor of 3 lower in winter than summer, providing a good match to US network observations of NH<sub>x</sub> (≡NH<sub>3</sub> gas + ammonium aerosol) and ammonium wet deposition fluxes. Model comparisons to observed deposition fluxes and surface air concentrations of oxidized nitrogen species (NO<sub>y</sub>) show overall good agreement but excessive wintertime HNO<sub>3</sub> production over the US Midwest and Northeast. This suggests a model overestimate N<sub>2</sub>O<sub>5</sub> hydrolysis in aerosols, and a possible factor is inhibition by aerosol nitrate. Model results indicate a total nitrogen deposition flux of 6.5 Tg N a<sup>−1</sup> over the contiguous US, including 4.2 as NO<sub>y</sub> and 2.3 as NH<sub>x</sub>. Domestic anthropogenic, foreign anthropogenic, and natural sources contribute respectively 78%, 6%, and 16% of total nitrogen deposition over the contiguous US in the model. The domestic anthropogenic contribution generally exceeds 70% in the east and in populated areas of the west, and is typically 50–70% in remote areas of the west. Total nitrogen deposition in the model exceeds 10 kg N ha<sup>−1</sup> a<sup>−1</sup> over 35% of the contiguous US

The Hasli Formation of the Irchel Plateau – A key record for older Early Pleistocene interglacial sediments in northern Switzerland

In the Alpine region of Central Europe, terrestrial Early Pleistocene deposits with preserved faunal and botanical remains are rare. The predominantly gravelly Höhere Deckenschotter (HDS) deposits of northern Switzerland and adjoining south-western Germany are considered the oldest Quaternary sediments in the northern Alpine Foreland, linked with the first extensive Quaternary Alpine glaciations. This multidisciplinary study investigates the Hasli Formation (HF), a unique silty unit with well-preserved biological remains within an HDS sequence at the Irchel Plateau north of Zürich, providing new climatic and environmental data for these exceptional deposits, as well as crucial information about their age. Systematic mapping of the HF, in addition to the underlying and covering gravel units, has been coupled with sedimentary logging and biostratigraphic analysis at several sites. The HF is present over an area c.4 by up to 1.4 km, and where studied is 1.6–6.2 m thick. The sediments and biological material are indicative of overbank deposits accumulating within the damp floodplain of a large meandering river. The recovered small mammal remains are from eight arvicolid species or genera, including Mimomys pliocaenicus, M. reidi/tigliensis and Clethrionomys cf. kretzoii, which became extinct c.1.8 Ma, and Pliomys episcopalis/simplicior, which first appeared c.2 Ma ago. The over 75k identified molluscs, include c.72k coming from 89 terrestrial species and over 3k from 28 aquatic taxa. The molluscan faunas from all locations where the HF has been studied share important biostratigraphic marker species, and indicate analogous climatic and environmental conditions. The marker species include several that became extinct during the Early Pleistocene, of which Clausilia stranzendorfensis and Cochlostoma salomoni, present throughout the HF, are the most important as they disappeared c.1.8 Ma. Many marker species have modern or palaeo-distributions that lie far to the west, south and east of the Swiss Plateau, showing that the climate was much warmer than today, typical for the Tiglian warm stage. The alluvial floodplain was covered by rather dense, mature woodland. Amino acid (AA) analysis shows that molluscan remains from the HF are among the oldest of the Quaternary shell material studied from across the Swiss Plateau. Palaeomagnetic data shows a change from reversed to normal polarity within the upper part of the HF. When combined, the small mammal and molluscan remains, palaeomagnetic measurements, AA geochronology and sedimentary data, suggest an age of 2.1–1.8 Ma for the HF. Recently produced cosmogenic dates bracket the age of the HDS gravels beneath the HF to depositional periods between 2.6 and 0.9 Ma, with the youngest ages being in disagreement with our findings. The abundance and diversity of the molluscs from the Irchel Plateau, with several rare extinct species, together with a notable small mammal assemblage, make this a key palaeontological site and an important reference point for European Quaternary biostratigraphy

Salivary concentrations of secretory leukocyte protease inhibitor and matrix metallopeptidase-9 following a single bout of exercise are associated with intensity and hydration status

AIM: To investigate the effects of exercise on salivary concentrations of inflammatory markers by analyzing a panel of 25 inflammatory markers in subjects who had participated in bicycle ergometer tests varying in workload and hydration status. METHODS: Fifteen healthy young men (20-35 years) had performed 4 different exercise protocols of 1 hour duration in a randomly assigned cross-over design, preceded by a rest protocol. Individual workloads depended on participant's pre-assessed individual maximum workload (Wmax): rest (protocol 1), 70% Wmax in hydrated (protocol 2) and dehydrated (protocol 3) state, 50% Wmax (protocol 4) and intermittent 85%/55% Wmax in 2 min blocks (protocol 5). Saliva samples were collected before (T0) and immediately after exercise (T1), and at several time points after exercise (2 hours (T3), 3 hours (T4), 6 hours (T5) and 24 hours (T6)). Secretory Leukocyte Protease Inhibitor (SLPI), Matrix Metallopeptidase-9 (MMP-9) and lactoferrin was analyzed using a commercial ELISA kit, a panel of 22 cytokines and chemokines were analyzed using a commercial multiplex immunoassay. Data was analyzed using a multilevel mixed linear model, with multiple test correction. RESULTS: Among a panel of 25 inflammatory markers, SLPI concentrations were significantly elevated immediately after exercise in all protocols compared to rest and higher concentrations reflected the intensity of exercise and hydration status. MMP-9 showed a significant increase in the 70% Wmax dehydrated, 50% Wmax and intermittent protocols. CONCLUSIONS: Salivary concentrations of SLPI and MMP-9 seem associated with exercise intensity and hydration status and may offer non-invasive biomarkers to study (local) inflammatory responses to different exercise intensities in human studies

Immunological Outcomes of Allergen-Specific Immunotherapy in Food Allergy

IgE-mediated food allergies are caused by adverse immunologic responses to food proteins. Allergic reactions may present locally in different tissues such as skin, gastrointestinal and respiratory tract and may result is systemic life-threatening reactions. During the last decades, the prevalence of food allergies has significantly increased throughout the world, and considerable efforts have been made to develop curative therapies. Food allergen immunotherapy is a promising therapeutic approach for food allergies that is based on the administration of increasing doses of culprit food extracts, or purified, and sometime modified food allergens. Different routes of administration for food allergen immunotherapy including oral, sublingual, epicutaneous and subcutaneous regimens are being evaluated. Although a wealth of data from clinical food allergen immunotherapy trials has been obtained, a lack of consistency in assessed clinical and immunological outcome measures presents a major hurdle for evaluating these new treatments. Coordinated efforts are needed to establish standardized outcome measures to be applied in food allergy immunotherapy studies, allowing for better harmonization of data and setting the standards for the future research. Several immunological parameters have been measured in food allergen immunotherapy, including allergen-specific immunoglobulin levels, basophil activation, cytokines, and other soluble biomarkers, T cell and B cell responses and skin prick tests. In this review we discuss different immunological parameters and assess their applicability as potential outcome measures for food allergen immunotherapy that may be included in such a standardized set of outcome measures

Minimally invasive application of botulinum toxin A in patients with idiopathic rhinitis

<p>Abstract</p> <p>Background</p> <p>Nasal hypersecretion due to idiopathic rhinitis can often not be treated sufficiently by conventional medication. Botulinum toxin A (BTA) has been injected into the nasal mucosa in patients with nasal hypersecretion with a reduction of rhinorrhea lasting for about 4 to 8 weeks. Since the nasal mucosa is well supplied with glands and vessels, the aim of this study was to find out if the distribution of BTA in the nasal mucosa and a reduction of nasal hypersecretion can also be reached by a minimally invasive application by sponges without an injection.</p> <p>Methods</p> <p>Patients were randomly divided into two groups. The effect of BTA (group A, C, D) or saline as placebo (group B) was investigated in 20 patients with idiopathic rhinitis by applying it with a sponge soaked with BTA (40 units each nostril) or saline. Subgroups C and D contained these patients of group A and B who did not improve in symptoms one week after the original treatment (either BTA or saline) who then received the alternative medication. Changes of symptoms (rhinorrhea, nasal obstruction) were scored by the patients in a four point scale and counted (consumption of tissues, sneezing) in a diary. The patients were followed up weeks 1, 2, 4, 8 and 12.</p> <p>Results</p> <p>There was a clear reduction of the amount of secretion in group A compared to group B, C and D. This did not correlate with the tissue consumption, which was comparably reduced in group A and B, but reduced less in group C and D. Sneezing was clearly reduced in group A but comparably unchanged in group B and C and increased in group D. Nasal congestion remained unchanged.</p> <p>Conclusion</p> <p>In some patients with therapy-resistant idiopathic rhinitis BTA applied with a sponge is a long-lasting and minimal invasive therapy to reduce nasal hypersecretion.</p

The RESET project: constructing a European tephra lattice for refined synchronisation of environmental and archaeological events during the last c. 100 ka

This paper introduces the aims and scope of the RESET project (. RESponse of humans to abrupt Environmental Transitions), a programme of research funded by the Natural Environment Research Council (UK) between 2008 and 2013; it also provides the context and rationale for papers included in a special volume of Quaternary Science Reviews that report some of the project's findings. RESET examined the chronological and correlation methods employed to establish causal links between the timing of abrupt environmental transitions (AETs) on the one hand, and of human dispersal and development on the other, with a focus on the Middle and Upper Palaeolithic periods. The period of interest is the Last Glacial cycle and the early Holocene (c. 100-8 ka), during which time a number of pronounced AETs occurred. A long-running topic of debate is the degree to which human history in Europe and the Mediterranean region during the Palaeolithic was shaped by these AETs, but this has proved difficult to assess because of poor dating control. In an attempt to move the science forward, RESET examined the potential that tephra isochrons, and in particular non-visible ash layers (cryptotephras), might offer for synchronising palaeo-records with a greater degree of finesse. New tephrostratigraphical data generated by the project augment previously-established tephra frameworks for the region, and underpin a more evolved tephra 'lattice' that links palaeo-records between Greenland, the European mainland, sub-marine sequences in the Mediterranean and North Africa. The paper also outlines the significance of other contributions to this special volume: collectively, these illustrate how the lattice was constructed, how it links with cognate tephra research in Europe and elsewhere, and how the evidence of tephra isochrons is beginning to challenge long-held views about the impacts of environmental change on humans during the Palaeolithic. © 2015 Elsevier Ltd.RESET was funded through Consortium Grants awarded by the Natural Environment Research Council, UK, to a collaborating team drawn from four institutions: Royal Holloway University of London (grant reference NE/E015905/1), the Natural History Museum, London (NE/E015913/1), Oxford University (NE/E015670/1) and the University of Southampton, including the National Oceanography Centre (NE/01531X/1). The authors also wish to record their deep gratitude to four members of the scientific community who formed a consultative advisory panel during the lifetime of the RESET project: Professor Barbara Wohlfarth (Stockholm University), Professor Jørgen Peder Steffensen (Niels Bohr Institute, Copenhagen), Dr. Martin Street (Romisch-Germanisches Zentralmuseum, Neuwied) and Professor Clive Oppenheimer (Cambridge University). They provided excellent advice at key stages of the work, which we greatly valued. We also thank Jenny Kynaston (Geography Department, Royal Holloway) for construction of several of the figures in this paper, and Debbie Barrett (Elsevier) and Colin Murray Wallace (Editor-in-Chief, QSR) for their considerable assistance in the production of this special volume.Peer Reviewe