Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data

International audienceA high quality dataset on the photo-oxidation of benzene, toluene, p-xylene and 1,3,5-trimethylbenzene has been obtained from experiments in the European Photoreactor (EUPHORE), a large outdoor environmental reaction chamber. The experiments were designed to test sensitive features of detailed aromatic mechanisms, and the dataset has been used to evaluate the performance of the Master Chemical Mechanism Version 3 (MCMv3). An updated version (MCMv3.1) was constructed based on recent experimental data, and details of its development are described in a companion paper. The MCMv3.1 aromatic mechanisms have also been evaluated using the EUPHORE dataset. Significant deficiencies have been identified in the mechanisms, in particular: 1) an over-estimation of the ozone concentration, 2) an under-estimation of the NO oxidation rate, 3) an under-estimation of OH. The use of MCMv3.1 improves the model-measurement agreement in some areas but significant discrepancies remain

Chemically-Mediated Roostmate Recognition and Roost Selection by Brazilian Free-Tailed Bats (Tadarida brasiliensis)

BACKGROUND: The Brazilian free-tailed bat (Tadarida brasiliensis) is an exceptionally social and gregarious species of chiropteran known to roost in assemblages that can number in the millions. Chemical recognition of roostmates within these assemblages has not been extensively studied despite the fact that an ability to chemically recognize individuals could play an important role in forming and stabilizing complex suites of social interactions. METHODOLOGY/PRINCIPAL FINDINGS: Individual bats were given a choice between three roosting pouches: one permeated with the scent of a group of roostmates, one permeated with the scent of non-roostmates, and a clean control. Subjects rejected non-roostmate pouches with greater frequency than roostmate pouches or blank control pouches. Also, bats chose to roost in the roostmate scented pouches more often than the non-roostmate or control pouches. CONCLUSIONS/SIGNIFICANCE: We demonstrated that T. brasiliensis has the ability to chemically recognize roostmates from non-roostmates and a preference for roosting in areas occupied by roostmates. It is important to investigate these behaviors because of their potential importance in colony dynamics and roost choice

Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography

Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, <i>p</i>-xylene and 1,3,5-trimethyl-benzene) with hydroxyl radicals in the presence of NO_x have been investigated using comprehensive gas chromatography (GCxGC). A GCxGC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE), a large volume outdoor reaction chamber in Valencia, Spain. Experiments were carried as part of the EXACT project (<b>E</b>ffects of the o<b>X</b>idation of <b>A</b>romatic <b>C</b>ompounds in the <b>T</b>roposphere). Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 minutes, allowing the evolution of species to be followed over oxidation periods of 3-6 hours. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards.<br> <br> For toluene reactions, observed oxygenated intermediates found included the co-eluting pair <font face='Symbol'>a</font>-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and <i>p</i>-methyl benzoquinone. In the <i>p</i>-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GCxGC for the measurement of the parent aromatics generally showed good agreement. Comparison of the concentrations observed by GCxGC to concentration-time profiles simulated using the Master Chemical Mechanism, MCMv3, demonstrates that this mechanism significantly over-predicts the concentrations of many product compounds and highlights the uncertainties which exist in our understanding of the atmospheric oxidation of aromatics

Iodine monoxide at a clean marine coastal site: observations of high frequency variations and inhomogeneous distributions

The first in situ point observations of iodine monoxide (IO) at a clean marine site were made using a laser-induced fluorescence instrument deployed at Mace Head, Ireland in August 2007. IO mixing ratios of up to 49.8 pptv (equivalent to pmol mol&lt;sup&gt;−1&lt;/sup&gt;; 1 s average) were observed at day-time low tide, well in excess of previous observed spatially-averaged maxima. A strong anti-correlation of IO mixing ratios with tide height was evident and the high time resolution of the observations showed IO peaked in the hour after low tide. The temporal delay in peak IO compared to low tide has not been observed previously but coincides with the time of peak aerosol number previously observed at Mace Head. &lt;br&gt;&lt;br&gt; A long path-differential optical absorption spectroscopy instrument (with a 2 × 6.8 km folded path across Roundstone Bay) was also based at the site for 3 days during the point measurement observation period. Both instruments show similar temporal trends but the point measurements of IO are a factor of ~6–10 times greater than the spatially averaged IO mixing ratios, providing direct empirical evidence of the presence of inhomogeneities in the IO mixing ratio near the intertidal region

Fast algorithms for histogram matching: Application to texture synthesis

Texture synthesis is the ability to create ensembles of images of similar structures from sample textures that have been photographed. The method we employ for texture synthesis is based on histogram matching of images at multiple scales and orientations. This paper reports two fast and in one case simple algorithms for histogram matching We show that the sort-matching and the optimal cumulative distribution function (CDF)-matching (OCM) algorithms provide high computational speed compared to that provided by the conventional approach. The sort-matching algorithm also provides exact histogram matching. Results of texture synthesis using either method show no subjective perceptual differences. The sort-matching algorithm is attractive because of its simplicity and speed, however as the size of the image increases, the OCM algorithm may be preferred for optimal computational speed

New Air Quality Targets & Interim Goals for Fine Particulate Matter – PM2.5: Implications for the West Midlands

This document provides a comprehensive overview of the implications of more stringent PM2.5 targets on air quality and public health in the West Midlands. By examining the sources and levels of PM2.5 pollution, exploring potential air quality scenarios and strategies, and estimating the health burden, this document seeks to inform stakeholders and decision makers in their efforts to improve air quality and reduce associated health risks and inequalities

Exposures to Particles and Volatile Organic Compounds across Multiple Transportation Modes

Travellers may be exposed to a wide range of different air pollutants during their journeys. In this study, personal exposures within vehicles and during active travel were tested in real-world conditions across nine different transport modes on journeys from London Paddington to Oxford City Centre, in the United Kingdom. The modes tested covered cycling, walking, buses, coaches, trains and private cars. Such exposures are relevant to questions of traveller comfort and safety in the context of airborne diseases such as COVID-19 and a growing awareness of the health, safety and productivity effects of interior air quality. Pollutants measured were particle number (PN), particle mass (PM), carbon dioxide (CO2) and speciated volatile organic compounds (VOCs), using devices carried on or with the traveller, with pumped sampling. Whilst only a relatively small number of journeys were assessed—inviting future work to assess their statistical significance—the current study highlights where a particular focus on exposure reduction should be placed. Real-time results showed that exposures were dominated by short-term spikes in ambient concentrations, such as when standing on a train platform, or at the roadside. The size distribution of particles varied significantly according to the situation. On average, the coach created the highest exposures overall; trains had mixed performance, while private cars and active transport typically had the lowest exposures. Sources of pollutants included both combustion products entering the vehicle and personal care products from other passengers, which were judged from desk research on the most likely source of each individual compound. Although more exposed to exhaust emissions while walking or cycling, the active traveller had the benefit of rapid dilution of these pollutants in the open air. An important variable in determining total exposure was the journey length, where the speed of the private car was advantageous compared to the relative slowness of the coach