Water-soluble organic aerosol in the Los Angeles Basin and outflow regions: Airborne and ground measurements during the 2010 CalNex field campaign

A particle-into-liquid sampler coupled to a total organic carbon analyzer (PILS-TOC) quantified particulate water-soluble organic carbon (WSOC) mass concentrations during the May 2010 deployment of the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) Twin Otter in the CalNex field study. WSOC data collected during 16 flights provide the first spatiotemporal maps of WSOC in the San Joaquin Valley, Los Angeles Basin, and outflow regions of the Basin. WSOC was consistently higher in concentration within the Los Angeles Basin, where sea breeze transport and Basin topography strongly influence the spatial distribution of WSOC. The highest WSOC levels were associated with fire plumes, highlighting the importance of both primary and secondary sources for WSOC in the region. Residual pollution layers enriched with WSOC are observed aloft up to an altitude of 3.2 km and the highest WSOC levels for each flight were typically observed above 500 m. Simultaneous ground WSOC measurements during aircraft overpasses in Pasadena and Riverside typically exhibit lower levels, especially when relative humidity (RH) was higher aloft suggestive of the influence of aerosol-phase water. This points to the underestimation of the radiative effects of WSOC when using only surface measurements. Reduced aerosol-phase water in the eastern desert outflow region likely promotes the re-partitioning of WSOC to the gas phase and suppression of processes to produce these species (partitioning, multiphase chemistry, photolytic production); as a result, WSOC is reduced relative to sulfate (but not as much as nitrate) as aerosol is advected from the Basin to the outflows

Secondary Organic Aerosol Coating Formation and Evaporation: Chamber Studies Using Black Carbon Seed Aerosol and the Single-Particle Soot Photometer

We report a protocol for using black carbon (BC) aerosol as the seed for secondary organic aerosol (SOA) formation in an environmental chamber. We employ a single-particle soot photometer (SP2) to probe single-particle SOA coating growth dynamics and find that SOA growth on nonspherical BC aerosol is diffusion-limited. Aerosol composition measurements with an Aerodyne high resolution time-of-flight aerosol mass spectrometer (AMS) confirm that the presence of BC seed does not alter the composition of SOA as compared to self-nucleated SOA or condensed SOA on ammonium sulfate seed. We employ a 3-wavelength photoacoustic soot spectrometer (PASS-3) to measure optical properties of the systems studied, including fullerene soot as the surrogate BC seed, nucleated naphthalene SOA from high-NO_x photooxidation, and nucleated α-pinene SOA from low-NO_x photooxidation. A core-and-shell Mie scattering model of the light absorption enhancement is in good agreement with measured enhancements for both the low- and high-NO_x α-pinene photooxidation systems, reinforcing the assumption of a core-shell morphology for coated BC particles. A discrepancy between measured and modeled absorption enhancement factors in the naphthalene photooxidation system is attributed to the wavelength-dependence of refractive index of the naphthalene SOA. The coating of high-NO_x α-pinene SOA decreases after reaching a peak thickness during irradiation, reflecting a volatility change in the aerosol, as confirmed by the relative magnitudes of f_(43) and f_(44) in the AMS spectra. The protocol described here provides a framework by which future studies of SOA optical properties and single-particle growth dynamics may be explored in environmental chambers

Composition and hygroscopicity of the Los Angeles Aerosol: CalNex

Aircraft-based measurements of aerosol composition, either bulk or single-particle, and both subsaturated and supersaturated hygroscopicity were made in the Los Angeles Basin and its outflows during May 2010 during the CalNex field study. Aerosol composition evolves from source-rich areas in the western Basin to downwind sites in the eastern Basin, evidenced by transition from an external to internal mixture, as well as enhancements in organic O : C ratio, the amount of organics and nitrate internally mixed on almost all particle types, and coating thickness on refractory black carbon (rBC). Transport into hot, dilute outflow regions leads to significant volatilization of semivolatile material, resulting in a unimodal aerosol comprising primarily oxygenated, low-volatility, water-soluble organics and sulfate. The fraction of particles with rBC or soot cores is between 27 and 51% based on data from a Single Particle Soot Photometer (SP2) and Aerosol Time of Flight Mass Spectrometer (ATOFMS). Secondary organics appear to inhibit subsaturated water uptake in aged particles, while CCN activity is enhanced with photochemical age. A biomass-burning event resulted in suppression of subsaturated hygroscopicity but enhancement in CCN activity, suggesting that BB particles may be nonhygroscopic at subsaturated RH but are important sources of CCN. Aerosol aging and biomass burning can lead to discrepancies between subsaturated and supersaturated hygroscopicity that may be related to mixing state. In the cases of biomass burning aerosol and aged particles coated with secondary material, more than a single parameter representation of subsaturated hygroscopicity and CCN activity is needed

Contrasting cloud composition between coupled and decoupled marine boundary layer clouds

Marine stratocumulus clouds often become decoupled from the vertical layer immediately above the ocean surface. This study contrasts cloud chemical composition between coupled and decoupled marine stratocumulus clouds for dissolved nonwater substances. Cloud water and droplet residual particle composition were measured in clouds off the California coast during three airborne experiments in July–August of separate years (Eastern Pacific Emitted Aerosol Cloud Experiment 2011, Nucleation in California Experiment 2013, and Biological and Oceanic Atmospheric Study 2015). Decoupled clouds exhibited significantly lower air-equivalent mass concentrations in both cloud water and droplet residual particles, consistent with reduced cloud droplet number concentration and subcloud aerosol (D_p > 100 nm) number concentration, owing to detachment from surface sources. Nonrefractory submicrometer aerosol measurements show that coupled clouds exhibit higher sulfate mass fractions in droplet residual particles, owing to more abundant precursor emissions from the ocean and ships. Consequently, decoupled clouds exhibited higher mass fractions of organics, nitrate, and ammonium in droplet residual particles, owing to effects of long-range transport from more distant sources. Sodium and chloride dominated in terms of air-equivalent concentration in cloud water for coupled clouds, and their mass fractions and concentrations exceeded those in decoupled clouds. Conversely, with the exception of sea-salt constituents (e.g., Cl, Na, Mg, and K), cloud water mass fractions of all species examined were higher in decoupled clouds relative to coupled clouds. Satellite and Navy Aerosol Analysis and Prediction System-based reanalysis data are compared with each other, and the airborne data to conclude that limitations in resolving boundary layer processes in a global model prevent it from accurately quantifying observed differences between coupled and decoupled cloud composition

In situ identification of Gram-negative bacteria in human lungs using a topical fluorescent peptide targeting lipid A

Acknowledgment to AAAS for publishing this manuscript with DOI 10.1126/scitranslmed.aal0033 https://www.science.org/doi/10.1126/scitranslmed.aal0033Respiratory infections in mechanically ventilated patients caused by Gram-negative bacteria are a major cause of morbidity. Rapid and unequivocal determination of the presence, localization, and abundance of bacteria is criti cal for positive resolution of the infections and could be used for patient stratification and for monitoring treat ment efficacy. Here, we developed an in situ approach to visualize Gram-negative bacterial species and cellular infiltrates in distal human lungs in real time. We used optical endomicroscopy to visualize a water-soluble optical imaging probe based on the antimicrobial peptide polymyxin conjugated to an environmentally sensitive fluoro phore. The probe was chemically stable and nontoxic and, after in-human intrapulmonary microdosing, enabled the specific detection of Gram-negative bacteria in distal human airways and alveoli within minutes. The results suggest that pulmonary molecular imaging using a topically administered fluorescent probe targeting bacterial lipid A is safe and practical, enabling rapid in situ identification of Gram-negative bacteria in humans.This work was supported by Wellcome Trust, the Department of Health Healthcare Innovation Challenge Fund (HICF-0510-069), and the Engineering and Physical Sciences Research Council Interdisciplinary Research Collaboration “Proteus” (EP/K03197X/1). The GMP activities were supported by the National Institute for Health Research (NIHR) BRC GMP Unit at Guy’s and St. Thomas’ NHS Foundation Trust and NIHR Biomedical Research Centre based at Guy’s and St. Thomas’ NHS Foundation Trust and King’s College London

Cerebral hypomyelination associated with biallelic variants of FIG4

The lipid phosphatase gene FIG4 is responsible for Yunisâ Varón syndrome and Charcotâ Marieâ Tooth disease Type 4J, a peripheral neuropathy. We now describe four families with FIG4 variants and prominent abnormalities of central nervous system (CNS) white matter (leukoencephalopathy), with onset in early childhood, ranging from severe hypomyelination to mild undermyelination, in addition to peripheral neuropathy. Affected individuals inherited biallelic FIG4 variants from heterozygous parents. Cultured fibroblasts exhibit enlarged vacuoles characteristic of FIG4 dysfunction. Two unrelated families segregate the same Gâ >â A variant in the +1 position of intron 21 in the homozygous state in one family and compound heterozygous in the other. This mutation in the splice donor site of exon 21 results in readâ through from exon 20 into intron 20 and truncation of the final 115 Câ terminal amino acids of FIG4, with retention of partial function. The observed CNS white matter disorder in these families is consistent with the myelination defects in the FIG4 null mouse and the known role of FIG4 in oligodendrocyte maturation. The families described here the expanded clinical spectrum of FIG4 deficiency to include leukoencephalopathy.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/149294/1/humu23720-sup-0001-Supp_Mat_Lenk_2018.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/149294/2/humu23720.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/149294/3/humu23720_am.pd

Nine-Year Effects of 3.7 Years of Intensive Glycemic Control on Cardiovascular Outcomes

In the Action to Control Cardiovascular Risk in Diabetes (ACCORD) trial, ∼4 years of intensive versus standard glycemic control in participants with type 2 diabetes and other cardiovascular risk factors had a neutral effect on the composite cardiovascular outcome, increased cardiovascular and total mortality, and reduced nonfatal myocardial infarction. Effects of the intervention during prolonged follow-up were analyzed

Phosphino-Triazole Ligands for Palladium-Catalyzed Cross-Coupling

Twelve 1,5-disubtituted and fourteen 5-substituted 1,2,3-triazole derivatives bearing diaryl or dialkyl phosphines at the 5-position were synthesized and used as ligands for palladium-catalyzed Suzuki–Miyaura cross-coupling reactions. Bulky substrates were tested, and lead-like product formation was demonstrated. The online tool SambVca2.0 was used to assess steric parameters of ligands and preliminary buried volume determination using XRD-obtained data in a small number of cases proved to be informative. Two modeling approaches were compared for the determination of the buried volume of ligands where XRD data was not available. An approach with imposed steric restrictions was found to be superior in leading to buried volume determinations that closely correlate with observed reaction conversions. The online tool LLAMA was used to determine lead-likeness of potential Suzuki–Miyaura cross-coupling products, from which 10 of the most lead-like were successfully synthesized. Thus, confirming these readily accessible triazole-containing phosphines as highly suitable ligands for reaction screening and optimization in drug discovery campaigns

Eastern Pacific Emitted Aerosol Cloud Experiment

Aerosol–cloud–radiation interactions are widely held to be the largest single source of uncertainty in climate model projections of future radiative forcing due to increasing anthropogenic emissions. The underlying causes of this uncertainty among modeled predictions of climate are the gaps in our fundamental understanding of cloud processes. There has been significant progress with both observations and models in addressing these important questions but quantifying them correctly is nontrivial, thus limiting our ability to represent them in global climate models. The Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) 2011 was a targeted aircraft campaign with embedded modeling studies, using the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft and the research vessel Point Sur in July and August 2011 off the central coast of California, with a full payload of instruments to measure particle and cloud number, mass, composition, and water uptake distributions. EPEACE used three emitted particle sources to separate particle-induced feedbacks from dynamical variability, namely 1) shipboard smoke-generated particles with 0.05–1-μm diameters (which produced tracks measured by satellite and had drop composition characteristic of organic smoke), 2) combustion particles from container ships with 0.05–0.2-μm diameters (which were measured in a variety of conditions with droplets containing both organic and sulfate components), and 3) aircraft-based milled salt particles with 3–5-μm diameters (which showed enhanced drizzle rates in some clouds). The aircraft observations were consistent with past large-eddy simulations of deeper clouds in ship tracks and aerosol– cloud parcel modeling of cloud drop number and composition, providing quantitative constraints on aerosol effects on warm-cloud microphysics