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

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

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

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

Vortex-core properties and vortex-lattice transformation in FeSe

Low-temperature scanning tunneling microscopy and spectroscopy has been used to image the vortex core and the vortex lattice in FeSe single crystals. The local tunneling spectra acquired at the center of elliptical vortex cores display a strong particle-hole asymmetry with spatial oscillation, characteristic of the quantum-limit vortex core. Furthermore, a quasihexagonal vortex lattice at low magnetic field undergoes noticeable rhombic distortions above a certain field ∼1.5 T. This field H∗ also reveals itself as a kink in the magnetic field dependence of the specific heat. The observation of a nearly hexagonal vortex lattice at low field is very surprising for materials with an orthorhombic crystal structure and it is in apparent contradiction with the elliptical shape of the vortex cores. These observations can be directly connected to the multiband nature of superconductivity in this material, provided we attribute them to the suppression of superconducting order parameter in one of the energy bands. Above the field H∗ the superconducting coherence length for this band can well exceed the intervortex distance which strengthens the nonlocal effects. Therefore, in addition to multiple-band effects, other possible sources that can contribute to the observed evolution of the vortex-lattice structure include nonlocal effects which cause the field-dependent interplay between the symmetry of the crystal and vortex lattice or the magnetoelastic interactions due to the strain field generated by vortices. © 2019 American Physical Society.Citrus Research and Development Foundation, CRDFGovernment Council on Grants, Russian FederationRussian Science Foundation, RSF: 17-12-01383, 18-72-10027Ministero dellâ Istruzione, dellâ Università e della Ricerca, MIURFoundation for the Advancement of Theoretical Physics and Mathematics: 17-11-109Ministero dellâ Istruzione, dellâ Università e della Ricerca, MIURKazan Federal UniversityOffice of Science, SCDivision of Materials Sciences and Engineering, DMSERussian Foundation for Basic Research, RFBR: 17-52-12044Ministry of Education and Science of the Russian Federation, MinobrnaukaTemple University, TUArgonne National Laboratory, ANLNanjing University of Science and Technology, NUST: K2-2017-084Drexel UniversityThe authors would like to acknowledge fruitful discussions with V. Kogan and T. Hanaguri. We also would like to acknowledge technical support during the early stage of these measurements from S. A. Moore. The work at Temple University, where low temperature scanning tunneling measurements were performed, was supported by US Department of Energy, Office of Science, Basic Energy Science, Materials Sciences and Engineering Division under Award No. DE-SC0004556. The work at Drexel University and at the M.V. Lomonosov Moscow State University was supported by the US Civilian Research and Development Foundation (CRDF Global). The work in Russia has been supported in part by the Ministry of Education and Science of the Russian Federation in the framework of the Increase Competitiveness Program of NUST MISiS Grant K2-2017-084, by Act 211 of the Government of Russian Federation, Contracts No. 02.A03.21.0004, No. 02.A03.21.0006, and No. 02.A03.21.0011 and by the Russian Government Program of Competitive Growth of Kazan Federal University. One of the authors (C.D.G.) would like to acknowledge partial support from MIUR (Ministry of Education, Universities and Research of the Italian Government). The work in IPM RAS (Nizhny Novgorod) was supported in part by the Russian Science Foundation (the calculation of the vortex-lattice characteristics Grant No. 18-72-10027; the calculation of the vortex-core deformation and the analysis of the experimental data Grant No. 17-12-01383), the Russian Foundation for Basic Research (Grant No. 17-52-12044), and Foundation for the Advancement of Theoretical Physics and Mathematics “BASIS” (Grant No. 17-11-109). The work at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Basic Energy Science, Materials Sciences and Engineering Division

Oxychlorine Species on Mars: The Gale Crater Story

Comparing data from the Alpha- Particle X-Ray Spectrometer (APXS) and the Sample Analysis at Mars (SAM) instruments on MSL reveals a strong linear correlation between chlorine and oxygen, further demonstrating the presence of oxychlorine species in Gale Crater and, very likely, globally on Mars. Perchlorate was first discovered on Mars by the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the Phoenix lander in 2008. Current hypotheses suggest that the formation of oxychlorine species such as perchlorate or chlorate is a global process and that these species should be globally distributed on Mars [e.g. 2-4]. To date, the SAM and Chemistry and Mineralogy (CheMin) instruments on MSL have analyzed one scooped sample of aeolian material (Rocknest [RN]), and four drilled samples (John Klein [JK], Cumberland [CB], Windjana [WJ], and Confidence Hills [CH]). The APXS instrument has also investigated the same or very similar samples. Although not definitively identified, oxychlorine species have been proposed to explain releases of O2, HCl, and chlorinated hydrocarbon species detected by evolved gas analysis (EGA) with the SAM instrument. We report a strong linear correlation between wt. % Cl detected by APXS and moles O2 detected by SAM during pyrolysis, indicating the presence of oxychlorine species in Gale Crater

Abiotic Input of Fixed Nitrogen by Bolide Impacts to Gale Crater During the Hesperian : Insights From the Mars Science Laboratory

We acknowledge the NASA Mars Science Laboratory Program, Centre National d'Études Spatiales, the Universidad Nacional Autónoma de México (PAPIIT IN109416, IN111619, and PAPIME PE103216), and the Consejo Nacional de Ciencia y Tecnología de México (CONACyT 220626) for their support. We thank Fred Calef for constructing Figure 4 and appreciate the interest and support received from John P. Grotzinger and Joy A. Crisp throughout the Curiosity mission. The authors are grateful to the SAM and MSL teams for successful operation of the SAM instrument and the Curiosity rover. The data used in this paper are listed in the supporting information, figures, and references. SAM Data contained in this paper are publicly available through the NASA Planetary Data System at http://pds‐geosciences.wustl.edu/missions/msl/sam.htm. We would like to express gratitude to Pierre‐Yves Meslin from the Research Institute in Astrophysics and Planetology at Toulouse, France, and five anonymous reviewers whose comments/suggestions on earlier drafts helped improve and clarify this manuscript. The authors declare no conflicts of interests.Peer reviewedPublisher PD

The state of the Martian climate

60°N was +2.0°C, relative to the 1981–2010 average value (Fig. 5.1). This marks a new high for the record. The average annual surface air temperature (SAT) anomaly for 2016 for land stations north of starting in 1900, and is a significant increase over the previous highest value of +1.2°C, which was observed in 2007, 2011, and 2015. Average global annual temperatures also showed record values in 2015 and 2016. Currently, the Arctic is warming at more than twice the rate of lower latitudes

Effect of petrochemical industrial emissions of reactive alkenes and NO\u3csub\u3ex\u3c/sub\u3e on tropospheric ozone formation in Houston, Texas

Petrochemical industrial facilities can emit large amounts of highly reactive hydrocarbons and NOx to the atmosphere; in the summertime, such colocated emissions are shown to consistently result in rapid and efficient ozone (O3) formation downwind. Airborne measurements show initial hydrocarbon reactivity in petrochemical source plumes in the Houston, TX, metropolitan area is primarily due to routine emissions of the alkenes propene and ethene. Reported emissions of these highly reactive compounds are substantially lower than emissions inferred from measurements in the plumes from these sources. Net O3 formation rates and yields per NOx molecule oxidized in these petrochemical industrial source plumes are substantially higher than rates and yields observed in urban or rural power plant plumes. These observations suggest that reductions in reactive alkene emissions from petrochemical industrial sources are required to effectively address the most extreme O3 exceedences in the Houston metropolitan area