Aerosol-cloud interactions remain the largest uncertainty in climate projections. Ultrafine aerosol particles smaller than 50 nanometers (UAP) can be abundant in the troposphere but are conventionally considered too small to affect cloud formation. Observational evidence and numerical simulations of deep convective clouds (DCCs) over the Amazon show that DCCs forming in a low-aerosol environment can develop very large vapor supersaturation because fast droplet coalescence reduces integrated droplet surface area and subsequent condensation. UAP from pollution plumes that are ingested into such clouds can be activated to form additional cloud droplets on which excess supersaturation condenses and forms additional cloud water and latent heating, thus intensifying convective strength. This mechanism suggests a strong anthropogenic invigoration of DCCs in previously pristine regions of the world.

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

Between 1 September and 4 October 2014, a combined airborne and ground-based measurement campaign was conducted to study tropical deep convective clouds over the Brazilian Amazon rain forest. The new German research aircraft, High Altitude and Long Range Research Aircraft (HALO), a modified Gulfstream G550, and extensive ground-based instrumentation were deployed in and near Manaus (State of Amazonas). The campaign was part of the German–Brazilian Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems–Cloud Processes of the Main Precipitation Systems in Brazil: A Contribution to Cloud Resolving Modeling and to the GPM (Global Precipitation Measurement) (ACRIDICON– CHUVA) venture to quantify aerosol–cloud–precipitation interactions and their thermodynamic, dynamic, and radiative effects by in situ and remote sensing measurements over Amazonia. The ACRIDICON–CHUVA field observations were carried out in cooperation with the second intensive operating period of Green Ocean Amazon 2014/15 (GoAmazon2014/5). In this paper we focus on the airborne data measured on HALO, which was equipped with about 30 in situ and remote sensing instruments for meteorological, trace gas, aerosol, cloud, precipitation, and spectral solar radiation measurements. Fourteen research flights with a total duration of 96 flight hours were performed. Five scientific topics were pursued: 1) cloud vertical evolution and life cycle (cloud profiling), 2) cloud processing of aerosol particles and trace gases (inflow and outflow), 3) satellite and radar validation (cloud products), 4) vertical transport and mixing (tracer experiment), and 5) cloud formation over forested/deforested areas. Data were collected in near-pristine atmospheric conditions and in environments polluted by biomass burning and urban emissions. The paper presents a general introduction of the ACRIDICON– CHUVA campaign (motivation and addressed research topics) and of HALO with its extensive instrument package, as well as a presentation of a few selected measurement results acquired during the flights for some selected scientific topics.

Acid-catalyzed multiphase chemistry of isoprene epoxydiols (IEPOX) on sulfate aerosol produces substantial amounts of water-soluble secondary organic aerosol (SOA) constituents, including 2-methyltetrols, methyltetrol sulfates, and oligomers thereof in atmospheric fine particulate matter (PM2.5). These constituents have commonly been measured by gas chromatography interfaced to electron ionization mass spectrometry (GC/EI-MS) with prior derivatization or by reverse-phase liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry (RPLC/ESI-HR-MS). However, both techniques have limitations in explicitly resolving and quantifying polar SOA constituents due either to thermal degradation or poor separation. With authentic 2-methyltetrol and methyltetrol sulfate standards synthesized in-house, we developed a hydrophilic interaction liquid chromatography (HILIC)/ESI-HR-quadrupole time-of-flight mass spectrometry (QTOFMS) protocol that can chromatographically resolve and accurately measure the major IEPOX-derived SOA constituents in both laboratory-generated SOA and atmospheric PM2.5. 2-Methyltetrols were simultaneously resolved along with 4-6 diastereomers of methyltetrol sulfate, allowing efficient quantification of both major classes of SOA constituents by a single non-thermal analytical method. The sum of 2-methyltetrols and methyltetrol sulfates accounted for approximately 92%, 62%, and 21% of the laboratory-generated β-IEPOX aerosol mass, laboratory-generated δ-IEPOX aerosol mass, and organic aerosol mass in the southeastern U.S., respectively, where the mass concentration of methyltetrol sulfates was 171-271% the mass concentration of methyltetrol. Mass concentrations of methyltetrol sulfates were 0.39 and 2.33 μg m-3 in a PM2.5 sample collected from central Amazonia and the southeastern U.S., respectively. The improved resolution clearly reveals isomeric patterns specific to methyltetrol sulfates from acid-catalyzed multiphase chemistry of β- and δ-IEPOX. We also demonstrate that conventional GC/EI-MS analyses overestimate 2-methyltetrols by up to 188%, resulting (in part) from the thermal degradation of methyltetrol sulfates. Lastly, C5-alkene triols and 3-methyltetrahydrofuran-3,4-diols are found to be largely GC/EI-MS artifacts formed from thermal degradation of 2-methyltetrol sulfates and 3-methyletrol sulfates, respectively, and are not detected with HILIC/ESI-HR-QTOFMS.

For the planningo fa no rganic synthesis route, the disconnection approach guided by retrosynthetic analysis of possible intermediates and the chemical reactions involved, backt or eady available starting materials, is well established. In contrast, such concepts just get developed for biocatalytic routes. In this Review we highlightf unctional group interconversions catalyzed by enzymes. The article is organized rather by chemical bonds formed-exemplified for CÀN, CÀO-and CÀC-bonds-and not by enzyme classes, covering ab road range of reactions to incorporate the desired functionality in the target molecule. Furthermore, the successful use of biocatalysts, also in combination with chemicals teps, is exemplified for the synthesis of various drugs and advanced pharmaceutical intermediates such as Crispine A, Sitagliptina nd Atorvastatin. This Reviewa lso provides some basic guidelines to choose the most appropriate enzyme for at argeted reaction keepingi nm ind aspects like commercial availability,c ofactor-requirement, solventt olerance, use of isolated enzymes or whole cell recombinant microorganisms aiming to assist organic chemists in the use of enzymesf or synthetic applications.

ABSTRACT:The impacts of El Niño (EN) on the rainfall over South America are investigated considering three EN types differing in the locations of the maximum sea surface temperature (SST) anomalies in the equatorial Pacific: the Central-Pacific (CP), Eastern-Pacific (EP) and the Mixed (MIX) types. The largest positive (SST) anomalies for the EP and CP types occur, respectively, in the eastern and central sectors of the tropical Pacific during all seasons. The SST anomaly pattern for the MIX-EN resembles that of the EP-EN during its onset stage, and of the CP-EN during its mature and demise stages. The different SST anomaly patterns affect the large-scale (Walker circulation and the tropospheric Rossby-wave trains) and local (South American low-level jet -SALLJ) atmospheric circulation patterns in different ways and lead to distinct precipitation anomaly patterns over South America. Variations in the position and longitudinal extension of the downward motions of the EN-related eastward-displaced Walker circulation explain the differences in the dryness over equatorial South America. For the CP-EN, a double Walker cell defines a more zonal configuration of the equatorial dryness over South America during the first three analysed seasons. This feature is not noted for the other two EN types. The Rossby-wave train pattern path depends on the EN types and seasons. In consequence, the associated local atmospheric circulation patterns depend also on the season and EN types. In all seasons, an intense SALLJ for the EP EN contrasts with weak or inexistence SALLJ for the other two EN types. Thus, a wetter condition over southeastern South America, southern and eastern Brazil occurs for the EP EN in relation to the other EN types. The results shown here, in particular considering the MIX EN type, have not been discussed before and might be useful mainly for climate monitoring purposes.

5-Hydroxymethylfurfural (5-HMF) is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Brønsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/glucose ratio is used. By contrast, we disclose in this work that the reaction of fructose in concentrated aqueous solutions of carboxylic acids, formic, acetic or lactic acids, used as reactive solvent media, leads to the selective dehydration of fructose in 5-HMF with yields up to 64% after 2 hours at 150 °C. This shows the potential of such solvent systems for the clean and easy production of 5-HMF from carbohydrates. The influence of adding solid catalysts to the carboxylic acid media was also reported, starting from glucose

Abstract. Routine cloud, precipitation and thermodynamic observations collected by the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) and Aerial Facility (AAF) during the 2-year US Department of Energy (DOE) ARM Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign are summarized. These observations quantify the diurnal to large-scale thermodynamic regime controls on the clouds and precipitation over the undersampled, climatically important Amazon basin region. The extended ground deployment of cloud-profiling instrumentation enabled a unique look at multiple cloud regimes at high temporal and vertical resolution. This longerterm ground deployment, coupled with two short-term aircraft intensive observing periods, allowed new opportunities to better characterize cloud and thermodynamic observational constraints as well as cloud radiative impacts for modeling efforts within typical Amazon "wet" and "dry" seasons.