Structure and toxicity of AZA-59, an azaspiracid shellfish poisoning toxin produced by Azadinium poporum (Dinophyceae)

To date, the putative shellfish toxin azaspiracid 59 (AZA-59) produced by Azadinium poporum (Dinophyceae) has been the only AZA found in isolates from the Pacific Northwest coast of the USA (Northeast Pacific Ocean). Anecdotal reports of sporadic diarrhetic shellfish poisoning-like illness, with the absence of DSP toxin or Vibrio contamination, led to efforts to look for other potential toxins, such as AZAs, in water and shellfish from the region. A. poporum was found in Puget Sound and the outer coast of Washington State, USA, and a novel AZA (putative AZA-59) was detected in low quantities in SPATT resins and shellfish. Here, an A. poporum strain from Puget Sound was mass-cultured and AZA-59 was subsequently purified and structurally characterized. In vitro cytotoxicity of AZA-59 towards Jurkat T lymphocytes and acute intraperitoneal toxicity in mice in comparison to AZA-1 allowed the derivation of a provisional toxicity equivalency factor of 0.8 for AZA-59. Quantification of AZA-59 using ELISA and LC-MS/MS yielded reasonable quantitative results when AZA-1 was used as an external reference standard. This study assesses the toxic potency of AZA-59 and will inform guidelines for its potential monitoring in case of increasing toxin levels in edible shellfish

Magnetic surface reconstruction in the van der Waals antiferromagnet Fe1+xTe

We acknowledge financial support from the EPSRC (EP/R031924/1 and EP/R032130/1) and NIST Center for Neutron Research. C.H. acknowledges support by the Austrian Science Fund (FWF) Project No. P32144-N36 and the VSC4 of the Vienna University of TechnologyFe1+xTe is a two-dimensional van der Waals antiferromagnet that becomes superconducting on anion substitution on the Te site. The properties of the parent phase of Fe1+xTe are sensitive to the amount of interstitial iron situated between the iron-tellurium layers. Fe1+xTe displays collinear magnetic order coexisting with low-temperature metallic resistivity for small concentrations of interstitial iron x and helical magnetic order for large values of x. While this phase diagram has been established through scattering [see, for example, E. E. Rodriguez et al., Phys. Rev. B 84, 064403 (2011); S. Rossler et al., ibid. 84, 174506 (2011)], recent scanning tunneling microscopy measurements [C. Trainer et al., Sci. Adv. 5, eaav3478 (2019)] have observed a different magnetic structure for small interstitial iron concentrations x with a significant canting of the magnetic moments along the crystallographic c axis of θ = 28° ± 3°. In this paper, we revisit themagnetic structure of Fe1.09Te using spherical neutron polarimetry and scanning tunneling microscopy to search for this canting in the bulk phase, and we compare surface and bulk magnetism. The results show that the bulk magnetic structure of Fe1.09Te is consistent with collinear in-plane order (θ= 0 with an error of ∼ 5°). Comparison with scanning tunneling microscopy on a series of Fe1+xTe samples reveals that the surface exhibits a magnetic surface reconstruction with a canting angle of the spins of θ = 29.8°. We suggest that this is a consequence of structural relaxation of the surface layer resulting in an out-of-plane magnetocrystalline anisotropy. The magnetism in Fe1+xTe displays different properties at the surface when the symmetry constraints of the bulk are removed.Publisher PDFPeer reviewe

Identification of Azadinium species and a new azaspiracid from Azadinium poporum in Puget Sound, Washington State, USA

The identification of a new suite of toxins, called azaspiracids (AZA), as the cause of human illnesses after the consumption of shellfish from the Irish west coast in 1995, resulted in interest in understanding the global distribution of these toxins and of species of the small dinoflagellate genus Azadinium, known to produce them. Clonal isolates of four species of Azadinium, A. poporum, A. cuneatum, A. obesum and A. dalianense were obtained from incubated sediment samples collected from Puget Sound, Washington State in 2016. These Azadinium species were identified using morphological characteristics confirmed by molecular phylogeny. Whereas AZA could not be detected in any strains of A. obesum, A. cuneatum and A. dalianense, all four strains of A. poporum produced a new azaspiracid toxin, based on LC–MS analysis, named AZA-59. The presence of AZA-59 was confirmed at low levels in situ using a solid phase resin deployed at several stations along the coastlines of Puget Sound. Using a combination of molecular methods for species detection and solid phase resin deployment to target shellfish monitoring of toxin at high-risk sites, the risk of azaspiracid shellfish poisoning can be minimized

Assessing a model of Pacific Northwest harmful algal bloom transport as a decision-support tool

In the Pacific Northwest, blooms of the diatom Pseudo-nitzschia (PN) sometimes produce domoic acid, a neurotoxin that causes amnesic shellfish poisoning, leading to a Harmful Algal Bloom (HAB) event. The Pacific Northwest (PNW) HAB Bulletin project, a partnership between academic, government, and tribal stakeholders, uses a combination of beach and offshore monitoring data and ocean forecast modeling to better understand the formation, evolution, and transport of HABs in this region. This project produces periodic Bulletins to inform local stakeholders of current and forecasted conditions. The goal of this study was to help improve how the forecast model is used in the Bulletin's preparation through a retrospective particle-tracking experiment. Using past observations of beach PN cell counts, events were identified that likely originated in the Juan de Fuca eddy, a known PN hotspot, and then particle tracks were used in the model to simulate these events. A variety of “beaching definitions” were tested, based on both water depth and distance offshore, to define when a particle in the model was close enough to the coast that it was likely to correspond to cells appearing in the intertidal zone and in shellfish diets, as well as a variety of observed PN cell thresholds to determine what cell count should be used to describe an event that would warrant further action. The skill of these criteria was assessed by determining the fraction of true positives, true negatives, false positives, and false negatives within the model in comparison with observations, as well as a variety of derived model performance metrics. This analysis suggested that for our stakeholders’ purposes, the most useful beaching definition is the 30 m isobath and the most useful PN cell threshold for coincident field-based sample PN density estimates is 10,000 PN cells/L. Lastly, the performance of a medium-resolution (1.5 km horizontal resolution) version of the model was compared with that of a high-resolution (0.5 km horizontal resolution) version, the latter currently used in forecasting for the PNW HAB Bulletin project. This analysis includes a direct comparison of the two model resolutions for one overlapping year (2017). These results suggested that a narrower, more realistic beaching definition is most useful in a high-resolution model, while a wider beaching definition is more appropriate in a lower resolution model like the medium-resolution version used in this analysis. Overall, this analysis demonstrated the importance of incorporating stakeholder needs into the statistical approach in order to generate the most effective decision-support information from oceanographic modeling

Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada

The NOAA WP-3 aircraft intercepted aged forest fire plumes from Alaska and western Canada during several flights of the NEAQS-ITCT 2k4 mission in 2004. Measurements of acetonitrile (CH3CN) indicated that the air masses had been influenced by biomass burning. The locations of the plume intercepts were well described using emissions estimates and calculations with the transport model FLEXPART. The best description of the data was generally obtained when FLEXPART injected the forest fire emissions to high altitudes in the model. The observed plumes were generally drier than the surrounding air masses at the same altitude, suggesting that the fire plumes had been processed by clouds and that moisture had been removed by precipitation. Different degrees of photochemical processing of the plumes were determined from the measurements of aromatic VOCs. The removal of aromatic VOCs was slow considering the transport times estimated from the FLEXPART model. This suggests that the average OH levels were low during the transport, which may be explained by the low humidity and high concentrations of carbon monoxide and other pollutants. In contrast with previous work, no strong secondary production of acetone, methanol and acetic acid is inferred from the measurements. A clear case of removal of submicron particle volume and acetic acid due to precipitation scavenging was observed. Copyright 2006 by the American Geophysical Union

Early Lung Function Abnormalities in Acromegaly.

BACKGROUND: Acromegaly is an insidious disorder caused by a pituitary growth hormone (GH)-secreting adenoma resulting in high circulating levels of GH and insulin-like growth factor I (IGF-I). Respiratory disorders are common complications in acromegaly, and can severely impact on quality of life, eventually affecting mortality. OBJECTIVES: The present study aimed to explore structural and functional lung alterations of acromegalic subjects. METHODS: We enrolled 10 consecutive patients (M/F: 5/5) affected by acromegaly. In all patients, magnetic resonance imaging (MRI) revealed the presence of pituitary tumor. All patients underwent clinical, lung functional, biological, and radiological assessments. Ten healthy age-matched subjects also served as controls. RESULTS: No statistically significant differences in lung function were detected between acromegalic and healthy subjects (p ≥ 0.05 for all analyses). However, the diffusing capacity for CO (TLCO) was significantly lower in the acromegalic group than in healthy subjects (TLCO% predicted: 78.1 ± 16 vs. 90 ± 6 %, respectively, p = 0.04; KCO% predicted: 77 ± 16 vs. 93 ± 5 %, p = 0.02, respectively). None of the lung function parameters correlated with duration of the disease, or with inflammatory marker of the airways. In acromegalics, biological (exhaled NO concentrations) and imaging (total lung volume, TLV, and mean lung density, MLD) evaluations were within normal values. The TLV measured by HRCT was 3540 ± 1555 ml in acromegalics, and the MLD was -711 ± 73 HU. None of the lung functional, radiological, and biological findings correlated with GH or IGF-I levels, and no correlation was found with duration of disease. CONCLUSIONS: In the current study, lung function evaluation allowed to detect early involvement of lung parenchyma, as assessed by TLCO and KCO, even in the absence of parenchymal density alterations of the lung by HRCT. These findings suggest to routinely include the carbon monoxide diffusing capacity in the lung function assessment for an early intervention in acromegaly

Anisotropic Superconducting Gaps and Boson Mode in FeSe 1−x Sx Single Crystals

Scanning tunneling spectroscopy has been used to investigate the superconducting gaps of FeSe 1−xSx single crystals and to reveal signatures of a bosonic mode in the quasiparticle density of states. We find that both superconducting gaps residing on different pockets of the Fermi surface are anisotropic. Moreover, the bosonic mode appears in the quasiparticle density of states as a redistribution of states at energy Ω/e, measured with respect to the superconducting gap. The energy of the boson mode Ω is found to scale with the superconducting gap, and it can be estimated to be in the range 2.6 ÷ 3.8 meV in agreement with a recent observation of a resonance spin excitation in neutron scattering. This suggests that quasiparticle interactions with this mode are important for superconductivity. © 2016, Springer Science+Business Media New York

Oxychlorine Detection in Gale Crater, Mars and Implications for Past Environmental Conditions

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity has analyzed 3 scooped samples and 15 drilled samples since landing in 2012. Oxychlorine compounds (perchlorate/chlorate) were detected in the first 9 drilled samples but have not been detected in the last 6, starting with the Oudam sample in the Hartmanns Valley member of the Murray formation (Table 1). Scooped samples have all contained detectable oxychlorine. These results suggest that oxychlorine formation and preservation spans the geologic record on Mars but has not been uniform spatially or temporally

Effectiveness of Metyrapone in Treating Cushing's Syndrome: A Retrospective Multicenter Study in 195 Patients

Background: Cushing's syndrome (CS) is a severe condition with excess mortality and significant morbidity necessitating control of hypercortisolemia. There are few data documenting use of the steroidogenesis inhibitor metyrapone for this purpose. Objective: The objective was to assess the effectiveness of metyrapone in controlling cortisol excess in a contemporary series of patients with CS. Design: This was designed as a retrospective, multicenter study. Setting: Thirteen University hospitals were studied. Patients: We studied a total of 195 patients with proven CS: 115 Cushing's disease, 37 ectopic ACTH syndrome, 43 ACTH-independent disease (adrenocortical carcinoma 10, adrenal adenoma 30, and ACTH-independent adrenal hyperplasia 3). Measurements: Measurements included biochemical parameters of activity of CS: mean serum cortisol “day-curve” (CDC) (target 150–300 nmol/L); 9 am serum cortisol; 24-hour urinary free cortisol (UFC). Results: A total of 164/195 received metyrapone monotherapy. Mean age was 49.6 ± 15.7 years; mean duration of therapy 8 months (median 3 mo, range 3 d to 11.6 y). There were significant improvements on metyrapone, first evaluation to last review: CDC (91 patients, 722.9 nmol/L [26.2 μg/dL] vs 348.6 nmol/L [12.6 μg/dL]; P < .0001); 9 am cortisol (123 patients, 882.9 nmol/L [32.0 μg/dL] vs 491.1 nmol/L [17.8 μg/dL]; P < .0001); and UFC (37 patients, 1483 nmol/24 h [537 μg/24 h] vs 452.6 nmol/24 h [164 μg/24 h]; P = .003). Overall, control at last review: 55%, 43%, 46%, and 76% of patients who had CDCs, UFCs, 9 am cortisol less than 331 nmol/L (12.0 μg/dL), and 9 am cortisol less than upper limit of normal/600 nmol/L (21.7 μg/dL). Median final dose: Cushing's disease 1375 mg; ectopic ACTH syndrome 1500 mg; benign adrenal disease 750 mg; and adrenocortical carcinoma 1250 mg. Adverse events occurred in 25% of patients, mostly mild gastrointestinal upset and dizziness, usually within 2 weeks of initiation or dose increase, all reversible. Conclusions: Metyrapone is effective therapy for short- and long-term control of hypercortisolemia in CS

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles