The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NO_x

The reaction of isoprene (C₅H₈) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NO_x) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔH_vap^eff), organic peroxide fraction, and the aerosol yield. <br><br> The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. However, reaction conditions did not favor the production of HO₂ radicals, thus allowing RO₂+RO₂ reactions to proceed more readily than if higher HO₂ levels had been generated. <br><br> SOA/SOC (i.e. OM/OC) was found to average 1.9 in the absence of NO_x. The effective enthalpy of vaporization was measured as 38.6 kJ mol^&minus;1, consistent with values used previously in modeling studies. The yields in this work (using an independent technique than used previously) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5–1.4% for carbon masses between 17 and 49 μgC m^&minus;3

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)

Potential of deep learning segmentation for the extraction of archaeological features from historical map series

Historical maps present a unique depiction of past landscapes, providing evidence for a wide range of information such as settlement distribution, past land use, natural resources, transport networks, toponymy and other natural and cultural data within an explicitly spatial context. Maps produced before the expansion of large‐scale mechanized agriculture reflect a landscape that is lost today. Of particular interest to us is the great quantity of archaeologically relevant information that these maps recorded, both deliberately and incidentally. Despite the importance of the information they contain, researchers have only recently begun to automatically digitize and extract data from such maps as coherent information, rather than manually examine a raster image. However, these new approaches have focused on specific types of information that cannot be used directly for archaeological or heritage purposes. This paper provides a proof of concept of the application of deep learning techniques to extract archaeological information from historical maps in an automated manner. Early twentieth century colonial map series have been chosen, as they provide enough time depth to avoid many recent large‐scale landscape modifications and cover very large areas (comprising several countries). The use of common symbology and conventions enhance the applicability of the method. The results show deep learning to be an efficient tool for the recovery of georeferenced, archaeologically relevant information that is represented as conventional signs, line‐drawings and text in historical maps. The method can provide excellent results when an adequate training dataset has been gathered and is therefore at its best when applied to the large map series that can supply such information. The deep learning approaches described here open up the possibility to map sites and features across entire map series much more quickly and coherently than other available methods, opening up the potential to reconstruct archaeological landscapes at continental scales

Lifeworld Inc. : and what to do about it

Can we detect changes in the way that the world turns up as they turn up? This paper makes such an attempt. The first part of the paper argues that a wide-ranging change is occurring in the ontological preconditions of Euro-American cultures, based in reworking what and how an event is produced. Driven by the security – entertainment complex, the aim is to mass produce phenomenological encounter: Lifeworld Inc as I call it. Swimming in a sea of data, such an aim requires the construction of just enough authenticity over and over again. In the second part of the paper, I go on to argue that this new world requires a different kind of social science, one that is experimental in its orientation—just as Lifeworld Inc is—but with a mission to provoke awareness in untoward ways in order to produce new means of association. Only thus, or so I argue, can social science add to the world we are now beginning to live in

Sea-land transitions in isopods: pattern of symbiont distribution in two species of intertidal isopods Ligia pallasii and Ligia occidentalis in the Eastern Pacific

Studies of microbial associations of intertidal isopods in the primitive genus Ligia (Oniscidea, Isopoda) can help our understanding of the formation of symbioses during sea-land transitions, as terrestrial Oniscidean isopods have previously been found to house symbionts in their hepatopancreas. Ligia pallasii and Ligia occidentalis co-occur in the high intertidal zone along the Eastern Pacific with a large zone of range overlap and both species showing patchy distributions. In 16S rRNA clone libraries mycoplasma-like bacteria (Firmicutes), related to symbionts described from terrestrial isopods, were the most common bacteria present in both host species. There was greater overall microbial diversity in Ligia pallasii compared with L. occidentalis. Populations of both Ligia species along an extensive area of the eastern Pacific coastline were screened for the presence of mycoplasma-like symbionts with symbiont-specific primers. Symbionts were present in all host populations from both species but not in all individuals. Phylogenetically, symbionts of intertidal isopods cluster together. Host habitat, in addition to host phylogeny appears to influence the phylogenetic relation of symbionts

Individual Preferences and Social Interactions Determine the Aggregation of Woodlice

n°e17389.info:eu-repo/semantics/publishe

Evaluation of Euler Fluxes for Hypersonic Heating Computations

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/83575/1/AIAA-41605-439.pd

Elucidating the molecular landscape of the stratum corneum

Characterization of the molecular structure of skin, especially the barrier layer, the stratum corneum, is a key research priority for generating understanding to improve diagnostics, aid pharmaceutical delivery, and prevent environmental damage. Our study uses the recently developed 3D OrbiSIMS technique to conduct in situ analysis of ex vivo human skin tissue and reveals the molecular chemistry of skin in unprecedented detail, as a result of the step change in high mass resolving power compared with previous studies. This characterization exposes the nonhomogeneity of the stratum corneum, both laterally and as a function of depth. Chemical variations relating to fundamental biological processes, such as the epidermal cholesterol sulfate cycle, are visualized using in situ analysis. We are able to resolve the debate around the chemical gradients present within the epidermis, for example, whether palmitic acid is of sebaceous origin or a true component of the stratum corneum. Through in situ depth analysis of cryogenically preserved samples, we are able to propose that it is actually a component of both surface sebum and the intrinsic lipid matrix. This approach also suggests similarity between the epidermis compounds found in human and porcine skin as a function of depth. Since porcine skin is a widely used model for permeation testing this result has clinical relevance. In addition to using this technique for endogenous species, we have used it to demonstrate the permeation of a commercially important antiaging peptide into the human stratum corneum. Due to its chemical similarity to native skin components and exceptionally low effective concentration, this information was previously unattainable

Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides

Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx