Large chemical characterisation of PM10 emitted from graphite material production: Application in source apportionment.

This work focuses on emissions from industrial sources that are still poorly understood in Europe, especially the "carbon industry". The study is based on two intensive sampling campaigns performed in a graphite material production plant for 2weeks in July 2013 and November 2013 in alpine valleys. The chemical characterization of PM10 was conducted at three sampling sites (outdoor and indoor sites) located inside one industrial area, which is considered as the highest emissions source of polycyclic aromatic hydrocarbons (PAHs) in the Arve valley. The identification of specific tracers among metals and trace elements is commonly used to characterize industrial emissions. In our study, original enrichment factors relative to the "rural exposed background" have been calculated, and the metallic fraction was not affected by this industrial source. In contrast, the organic fraction of PM10 has a number of features, providing a complete organic source profile and referred to as the "carbon industry". In particular, polycyclic aromatic sulfur heterocycles (PASH) have been largely detected from fugitive emissions with rather large concentrations. The average concentrations of benzo(b)naphtho(2,1-d)thiophene (BNT(2,1)) reached 2.35-6.56ng·m(-3) and 60.5-376ng·m(-3) for outdoor and indoor sites, respectively. The use of this reference profile in the chemical mass balance model (CMB) applied to samples collected in two sites near industrial areas shows that this source had an average contribution of 6% of the organic matter (OM) mass during the sampling period during the winter of 2013.

Source apportionment of PM10, organic carbon and elemental carbon at Swiss sites: an intercomparison of different approaches.

In this study, the results of source apportionment of particulate matter (PM10), organic carbon (OC), and elemental carbon (EC) - as obtained through different approaches at different types of sites (urban background, urban roadside, and two rural sites in Switzerland) - are compared. The methods included in this intercomparison are positive matrix factorisation modelling (PMF, applied to chemical composition data including trace elements, inorganic ions, OC, and EC), molecular marker chemical mass balance modelling (MM-CMB), and the aethalometer model (AeM). At all sites, the agreement of the obtained source contributions was reasonable for OC, EC, and PM10. Based on an annual average, and at most of the considered sites, secondary organic carbon (SOC) is the component with the largest contribution to total OC; the most important primary source of OC is wood combustion, followed by road traffic. Secondary aerosols predominate in PM10. All considered techniques identified road traffic as the dominant source of EC, while wood combustion emissions are of minor importance for this constituent. The intercomparison of different source apportionment approaches is helpful to identify the strengths and the weaknesses of the different methods. Application of PMF has limitations when source emissions have a strong temporal correlation, or when meteorology has a strong impact on PM variability. In these cases, the use of PMF can result in mixed source profiles and consequently in the under- or overestimation of the real-world sources. The application of CMB models can be hampered by the unavailability of source profiles and the non-representativeness of the available profiles for local source emissions. This study also underlines that chemical transformations of molecular markers in the atmosphere can lead to the underestimation of contributions from primary sources, in particular during the summer period or when emission sources are far away from the receptor sites.

Field comparison of particulate PAH measurements using a low-flow denuder device and conventional sampling systems.

Polyaromatic hydrocarbons (PAHs) are complex carbonaceous compounds emitted to the atmosphere by various combustion processes. Because the toxicity of many of them is now well recognized and documented, the determination of their atmospheric concentrations is of great interest to better understand and develop future atmospheric pollution control strategies. Hence, a common sampling protocol has to be defined to homogenize the results. With this goal in mind, field studies were carried out under different environmental conditions (74 samples) by simultaneously operating both a conventional sampler and a sampler equipped with a denuder tube upstream from the filter. The experimental results presented in this work show that the atmospheric particulate PAH concentrations are underestimated at least by a factor of 2 using a conventional sampler. The discrepancy between the two kinds of samplers used varied a lot from one compound to another and from one field campaign to another. This discrepancy may be explained by a simple degradation of particulate PAH in the natural atmosphere and on the filter. This is particularly worrisome because, based on the results presented in this work, the atmospheric PAH concentrations measured using conventional samplers not equipped with an ozone trap can underestimate the PAH concentration by more than 200%. This is especially true when the samples are collected in the vicinity of the point source of particulate PAHs and for highly reactive compounds such as benzo[a]pyrene.

Improvement of poly(amphiphilic pyrrole) enzyme electrodes via the incorporation of synthetic laponite-clay-nanoparticles.

The electropolymerization of an enzyme-amphiphilic pyrrole ammonium-laponite nanoparticles mixture preadsorbed on the electrode surface provides the simultaneous immobilization of the enzyme and the hydrophilic laponite-clay-nanoparticles in a functionalized polypyrrole film. The presence of incorporated laponite particles within the electrogenerated polymer induces a strong improvement of the analytical performances (I(max) and sensitivity) of amperometric biosensors based on polyphenol oxidase. These beneficial effects have been attributed to a marked enhancement of the apparent specific activity of the immobilized enzyme (from 0.21 to 0.85% of the specific activity of the free enzyme), the permeability of the host polymer being unchanged. This strategy of biosensor performance improvement was tested with cholesterol oxidase as an enzyme model. The presence of laponite additive in the poly(amphiphilic pyrrole) host matrix induces a similar enhancement of sensitivity and I(max) for cholesterol biosensing as well as a large improvement of the storage stability of the polypyrrole-cholesterol oxidase electrode.