Modeling of the formation of short-chain acids in propane flames

International audienceIn order to better understand their potential formation in combustion systems, a detailed kinetic mechanism for the formation of short-chain monocarboxylic acids, formic (HCOOH), acetic (CH3COOH), propionic (C2H5COOH) and propenic (C2H3COOH)) acids, has been developed. Simulations of lean (equivalence ratios from 0.9 to 0.48) laminar premixed flames of propane stabilized at atmospheric pressure with nitrogen as diluent have been performed. It was found that amounts up to 25 ppm of acetic acid, 15 ppm of formic acid and 1 ppm of C3 acid can be formed for some positions in the flames. Simulations showed that the more abundant C3 acid formed is propenic acid. A quite acceptable agreement has been obtained with the scarce results from the literature concerning oxygenated compounds, including aldehydes (CH2O, CH3CHO) and acids. A reaction pathways analysis demonstrated that each acid is mainly derived from the aldehyde of similar structure

To better understand the formation of short-chain acids in combustion systems

International audienceOur study aims at a better control and understanding of the transfer of a complex [DNA supercoiled plasmid - dodecyltrimethylammonium surfactant] layer from a liquid-vapour water interface onto a silicon surface without any additional cross-linker. The production of the complexed layer and its transfer from the aqueous subphase to the substrate is achieved with a Langmuir-Blodgett device. The substrate consists of a reconstructed boron doped silicon substrate with a nanometer-scale roughness. Using X-ray photoelectron spectroscopy and atomic force microscopy measurements, it is shown that the DNA complexes are stretched in a disorderly manner throughout a 2-4 nm high net-like structure. The mechanism of transfer of this layer onto the planar surface of the semi-conductor and the parameters of the process are analysed and illustrated by atomic force microscopy snapshots. The molecular layer exhibits the typical characteristics of a spinodal decomposition pattern or dewetting features. Plasmid molecules appear like long flattened fibers covering the surface, forming holes of various shapes and areas. The cluster-cluster aggregation of the complex structure gets very much denser on the substrate edge. The supercoiled DNA plasmids undergo conformational changes and a high degree of condensation and aggregation is observed

ECOC comparison exercise with identical thermal protocols after temperature offset correction - Instrument diagnostics by in-depth evaluation of operational parameters

© Author(s) 2015. A comparison exercise on thermal-optical elemental carbon/organic carbon (ECOC) analysers was carried out among 17 European laboratories. Contrary to previous comparison exercises, the 17 participants made use of an identical instrument set-up, after correcting for temperature offsets with the application of a recently developed temperature calibration kit (Sunset Laboratory Inc, OR, US). Temperature offsets reported by participants ranged from -93 to +100 °C per temperature step. Five filter samples and two sucrose solutions were analysed with both the EUSAAR2 and NIOSH870 thermal protocols. z scores were calculated for total carbon (TC); nine outliers and three stragglers were identified. Three outliers and eight stragglers were found for EC. Overall, the participants provided results between the warning levels with the exception of two laboratories that showed poor performance, the causes of which were identified and corrected through the course of the comparison exercise. The TC repeatability and reproducibility (expressed as relative standard deviations) were 11 and 15% for EUSAAR2 and 9.2 and 12% for NIOSH870; the standard deviations for EC were 15 and 20% for EUSAAR2 and 20 and 26% for NIOSH870. TC was in good agreement between the two protocols, TCNIOSH870 =0.98 × TCEUSAAR2 (R2 = 1.00, robust means). Transmittance (TOT) calculated EC for NIOSH870 was found to be 20% lower than for EUSAAR2, ECNIOSH870 = 0.80 × ECEUSAAR2 (R2 = 0.96, robust means). The thermograms and laser signal values were compared and similar peak patterns were observed per sample and protocol for most participants. Notable deviations from the typical patterns indicated either the absence or inaccurate application of the temperature calibration procedure and/or pre-oxidation during the inert phase of the analysis. Low or zero pyrolytic organic carbon (POC), as reported by a few participants, is suggested as an indicator of an instrument-specific pre-oxidation. A sample-specific pre-oxidation effect was observed for filter G, for all participants and both thermal protocols, indicating the presence of oxygen donors on the suspended particulate matter. POC (TOT) levels were lower for NIOSH870 than for EUSAAR2, which is related to the heating profile differences of the two thermal protocols

A European aerosol phenomenology -4: Harmonized concentrations of carbonaceous aerosol at 10 regional background sites across Europe

Although particulate organic and elemental carbon (OC and EC) are important constituents of the suspended atmospheric particulate matter (PM), measurements of OC and EC are much less common and more uncertain than measurements of e.g. the ionic components of PM. In the framework of atmospheric research infrastructures supported by the European Union, actions have been undertaken to determine and mitigate sampling artefacts, and assess the comparability of OC and EC data obtained in a network of 10 atmospheric observatories across Europe. Positive sampling artefacts (from 0.4 to 2.8 μg C/m3) and analytical discrepancies (between −50% and +40% for the EC/TC ratio) have been taken into account to generate a robust data set, from which we established the phenomenology of carbonaceous aerosols at regional background sites in Europe. Across the network, TC and EC annual average concentrations range from 0.4 to 9 μg C/m3, and from 0.1 to 2 μg C/m3, respectively. TC/PM10 annual mean ratios range from 0.11 at a Mediterranean site to 0.34 at the most polluted continental site, and TC/PM2.5 ratios are slightly greater at all sites (0.15–0.42). EC/TC annual mean ratios range from 0.10 to 0.22, and do not depend much on PM concentration levels, especially in winter. Seasonal variations in PM and TC concentrations, and in TC/PM and EC/TC ratios, differ across the network, which can be explained by seasonal changes in PM source contributions at some sites

In situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris megacity

A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70 % of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20 % in winter and 40 % in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies

Emission factors and detailed chemical characterization of PM and VOCs from 4 in-use petrol and diesel passenger cars

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Influence of the renewal of residential wood stoves on the PM biomass burning contribution in a French Alps valley

International audienc

Evaluation of a residential wood heating emissions abatement policy at local scale in a complex area, the Arve valley, France.

International audienc