PM10-bound trace elements in pan-European urban atmosphere.

Although many studies have discussed the impact of Europe's air quality, very limited research focused on the detailed phenomenology of ambient trace elements (TEs) in PM10 in urban atmosphere. This study compiled long-term (2013-2022) measurements of speciation of ambient urban PM10 from 55 sites of 7 countries (Switzerland, Spain, France, Greece, Italy, Portugal, UK), aiming to elucidate the phenomenology of 20 TEs in PM10 in urban Europe. The monitoring sites comprised urban background (UB, n = 26), traffic (TR, n = 10), industrial (IN, n = 5), suburban background (SUB, n = 7), and rural background (RB, n = 7) types. The sampling campaigns were conducted using standardized protocols to ensure data comparability. In each country, PM10 samples were collected over a fixed period using high-volume air samplers. The analysis encompassed the spatio-temporal distribution of TEs, and relationships between TEs at each site. Results indicated an annual average for the sum of 20 TEs of 90 ± 65 ng/m3, with TR and IN sites exhibiting the highest concentrations (130 ± 66 and 131 ± 80 ng/m3, respectively). Seasonal variability in TEs concentrations, influenced by emission sources and meteorology, revealed significant differences (p < 0.05) across all monitoring sites. Estimation of TE concentrations highlighted distinct ratios between non-carcinogenic and carcinogenic metals, with Zn (40 ± 49 ng/m3), Ti (21 ± 29 ng/m3), and Cu (23 ± 35 ng/m3) dominating non-carcinogenic TEs, while Cr (5 ± 7 ng/m3), and Ni (2 ± 6 ng/m3) were prominent among carcinogenic ones. Correlations between TEs across diverse locations and seasons varied, in agreement with differences in emission sources and meteorological conditions. This study provides valuable insights into TEs in pan-European urban atmosphere, contributing to a comprehensive dataset for future environmental protection policies.

Recommendations for reporting equivalent black carbon (eBC) mass concentrations based on long-term pan-European in-situ observations.

A reliable determination of equivalent black carbon (eBC) mass concentrations derived from filter absorption photometers (FAPs) measurements depends on the appropriate quantification of the mass absorption cross-section (MAC) for converting the absorption coefficient (babs) to eBC. This study investigates the spatial-temporal variability of the MAC obtained from simultaneous elemental carbon (EC) and babs measurements performed at 22 sites. We compared different methodologies for retrieving eBC integrating different options for calculating MAC including: locally derived, median value calculated from 22 sites, and site-specific rolling MAC. The eBC concentrations that underwent correction using these methods were identified as LeBC (local MAC), MeBC (median MAC), and ReBC (Rolling MAC) respectively. Pronounced differences (up to more than 50 %) were observed between eBC as directly provided by FAPs (NeBC; Nominal instrumental MAC) and ReBC due to the differences observed between the experimental and nominal MAC values. The median MAC was 7.8 ± 3.4 m2 g-1 from 12 aethalometers at 880 nm, and 10.6 ± 4.7 m2 g-1 from 10 MAAPs at 637 nm. The experimental MAC showed significant site and seasonal dependencies, with heterogeneous patterns between summer and winter in different regions. In addition, long-term trend analysis revealed statistically significant (s.s.) decreasing trends in EC. Interestingly, we showed that the corresponding corrected eBC trends are not independent of the way eBC is calculated due to the variability of MAC. NeBC and EC decreasing trends were consistent at sites with no significant trend in experimental MAC. Conversely, where MAC showed s.s. trend, the NeBC and EC trends were not consistent while ReBC concentration followed the same pattern as EC. These results underscore the importance of accounting for MAC variations when deriving eBC measurements from FAPs and emphasize the necessity of incorporating EC observations to constrain the uncertainty associated with eBC.

Characterizing the sources of ambient PM10 organic aerosol in urban and rural Catalonia, Spain.

Organic aerosols (OA) have recently been shown to be the dominant contributor to the oxidative potential of airborne particulate matter in northeastern Spain. We collected PM10 filter samples every fourth day from January 2017 to March 2018 at two sampling stations located in Barcelona city and Montseny Natural Park, representing urban and rural areas, respectively. The chemical composition of PM10 was analyzed offline using a broad set of analytical instruments, including high-resolution time-of-flight mass spectrometry (HR-ToF-AMS), a total organic carbon analyzer (TCA), inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), and thermal-optical carbon analyzer. Source apportionment analysis of the water-soluble organic content of the samples measured via HR-ToF-AMS revealed two primary and two secondary sources of OA, which included biomass-burning OA (BBOA), sulfur-containing OA (SCOA), as well as summer- and winter­oxygenated OA (SOOA and WOOA). The presence of hydrocarbon-like water-insoluble OA was also identified based on concentration trends in black carbon and nitrogen oxides. The results from the source apportionment analysis of the inorganic composition were correlated with different OA factors to assess potential source contributors. Barcelona showed significantly higher average water-soluble OA concentrations (5.63 ± 0.56 µg m-3) than Montseny (3.27 ± 0.37 µg m-3) over the sampling period. WOOA accounted for nearly 27 % of the averaged OA in Barcelona compared to only 7 % in Montseny. In contrast, SOOA had a greater contribution to OA in Montseny (47 %) than in Barcelona (24 %). SCOA and BBOA were responsible for 15-28 % of the OA at both sites. There were also seasonal variations in the relative contributions of different OA sources. Our overall results showed that local anthropogenic sources were primarily responsible for up to 70 % of ambient soluble OA in Barcelona, and regulating local-scale emissions could significantly improve air quality in urban Spain.

The variability of mass concentrations and source apportionment analysis of equivalent black carbon across urban Europe.

This study analyzed the variability of equivalent black carbon (eBC) mass concentrations and their sources in urban Europe to provide insights into the use of eBC as an advanced air quality (AQ) parameter for AQ standards. This study compiled eBC mass concentration datasets covering the period between 2006 and 2022 from 50 measurement stations, including 23 urban background (UB), 18 traffic (TR), 7 suburban (SUB), and 2 regional background (RB) sites. The results highlighted the need for the harmonization of eBC measurements to allow for direct comparisons between eBC mass concentrations measured across urban Europe. The eBC mass concentrations exhibited a decreasing trend as follows: TR > UB > SUB > RB. Furthermore, a clear decreasing trend in eBC concentrations was observed in the UB sites moving from Southern to Northern Europe. The eBC mass concentrations exhibited significant spatiotemporal heterogeneity, including marked differences in eBC mass concentration and variable contributions of pollution sources to bulk eBC between different cities. Seasonal patterns in eBC concentrations were also evident, with higher winter concentrations observed in a large proportion of cities, especially at UB and SUB sites. The contribution of eBC from fossil fuel combustion, mostly traffic (eBCT) was higher than that of residential and commercial sources (eBCRC) in all European sites studied. Nevertheless, eBCRC still had a substantial contribution to total eBC mass concentrations at a majority of the sites. eBC trend analysis revealed decreasing trends for eBCT over the last decade, while eBCRC remained relatively constant or even increased slightly in some cities.

Ambient air particulate total lung deposited surface area (LDSA) levels in urban Europe.

This study aims to picture the phenomenology of urban ambient total lung deposited surface area (LDSA) (including head/throat (HA), tracheobronchial (TB), and alveolar (ALV) regions) based on multiple path particle dosimetry (MPPD) model during 2017-2019 period collected from urban background (UB, n = 15), traffic (TR, n = 6), suburban background (SUB, n = 4), and regional background (RB, n = 1) monitoring sites in Europe (25) and USA (1). Briefly, the spatial-temporal distribution characteristics of the deposition of LDSA, including diel, weekly, and seasonal patterns, were analyzed. Then, the relationship between LDSA and other air quality metrics at each monitoring site was investigated. The result showed that the peak concentrations of LDSA at UB and TR sites are commonly observed in the morning (06:00-8:00 UTC) and late evening (19:00-22:00 UTC), coinciding with traffic rush hours, biomass burning, and atmospheric stagnation periods. The only LDSA night-time peaks are observed on weekends. Due to the variability of emission sources and meteorology, the seasonal variability of the LDSA concentration revealed significant differences (p = 0.01) between the four seasons at all monitoring sites. Meanwhile, the correlations of LDSA with other pollutant metrics suggested that Aitken and accumulation mode particles play a significant role in the total LDSA concentration. The results also indicated that the main proportion of total LDSA is attributed to the ALV fraction (50 %), followed by the TB (34 %) and HA (16 %). Overall, this study provides valuable information of LDSA as a predictor in epidemiological studies and for the first time presenting total LDSA in a variety of European urban environments.

Phenomenology of ultrafine particle concentrations and size distribution across urban Europe.

The 2017-2019 hourly particle number size distributions (PNSD) from 26 sites in Europe and 1 in the US were evaluated focusing on 16 urban background (UB) and 6 traffic (TR) sites in the framework of Research Infrastructures services reinforcing air quality monitoring capacities in European URBAN & industrial areaS (RI-URBANS) project. The main objective was to describe the phenomenology of urban ultrafine particles (UFP) in Europe with a significant air quality focus. The varying lower size detection limits made it difficult to compare PN concentrations (PNC), particularly PN10-25, from different cities. PNCs follow a TR > UB > Suburban (SUB) order. PNC and Black Carbon (BC) progressively increase from Northern Europe to Southern Europe and from Western to Eastern Europe. At the UB sites, typical traffic rush hour PNC peaks are evident, many also showing midday-morning PNC peaks anti-correlated with BC. These peaks result from increased PN10-25, suggesting significant PNC contributions from nucleation, fumigation and shipping. Site types to be identified by daily and seasonal PNC and BC patterns are: (i) PNC mainly driven by traffic emissions, with marked correlations with BC on different time scales; (ii) marked midday/morning PNC peaks and a seasonal anti-correlation with PNC/BC; (iii) both traffic peaks and midday peaks without marked seasonal patterns. Groups (ii) and (iii) included cities with high insolation. PNC, especially PN25-800, was positively correlated with BC, NO2, CO and PM for several sites. The variable correlation of PNSD with different urban pollutants demonstrates that these do not reflect the variability of UFP in urban environments. Specific monitoring of PNSD is needed if nanoparticles and their associated health impacts are to be assessed. Implementation of the CEN-ACTRIS recommendations for PNSD measurements would provide comparable measurements, and measurements of <10 nm PNC are needed for full evaluation of the health effects of this size fraction.

European aerosol phenomenology - 8: Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets.

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.

Variability of the Atmospheric PM10 Microbiome in Three Climatic Regions of France.

Primary Biogenic Organic Aerosols (PBOA) were recently shown to be produced by only a few types of microorganisms, emitted by the surrounding vegetation in the case of a regionally homogeneous field site. This study presents the first comprehensive description of the structure and main sources of airborne microbial communities associated with temporal trends in Sugar Compounds (SC) concentrations of PM10 in 3 sites under a climatic gradient in France. By combining sugar chemistry and DNA Metabarcoding approaches, we intended to identify PM10-associated microbial communities and their main sources at three sampling-sites in France, under different climates, during the summer of 2018. This study accounted also for the interannual variability in summer airborne microbial community structure (bacteria and fungi only) associated with PM10-SC concentrations during a 2 consecutive years' survey at one site. Our results showed that temporal changes in PM10-SC in the three sites are associated with the abundance of only a few specific taxa of airborne fungi and bacterial. These taxa differ significantly between the 3 climatic regions studied. The microbial communities structure associated with SC concentrations of PM10 during a consecutive 2-year study remained stable in the rural area. Atmospheric concentration levels of PM10-SC species varied significantly between the 3 study sites, but with no clear difference according to site typology (rural vs. urban), suggesting that SC emissions are related to regional rather than local climatic characteristics. The overall microbial beta diversity in PM10 samples is significantly different from that of the main vegetation around the urban sites studied. This indicates that the airborne microorganisms at these urban sites are not solely from the immediate surrounding vegetation, which contrasts with observations at the scale of a regionally homogeneous rural site in 2017. These results improve our understanding of the spatial behavior of tracers of PBOA emission sources, which need to be better characterized to further implement this important mass fraction of Organic Matter (OM) in Chemical Transport models (CTM).

Leader-Following Consensus and Formation Control of VTOL-UAVs with Event-Triggered Communications †.

This article presents the design and implementation of an event-triggered control approach, applied to the leader-following consensus and formation of a group of autonomous micro-aircraft with capabilities of vertical take-off and landing (VTOL-UAVs). The control strategy is based on an inner-outer loop control approach. The inner control law stabilizes the attitude and position of one agent, whereas the outer control follows a virtual leader to achieve position consensus cooperatively through an event-triggered policy. The communication topology uses undirected and connected graphs. With such an event-triggered control, the closed-loop trajectories converge to a compact sphere, centered in the origin of the error space. Furthermore, the minimal inter-sampling time is proven to be below bounded avoiding the Zeno behavior. The formation problem addresses the group of agents to fly in a given shape configuration. The simulation and experimental results highlight the performance of the proposed control strategy.

Effect of Stove Technology and Combustion Conditions on Gas and Particulate Emissions from Residential Biomass Combustion.

We have systematically examined the gas and particle phase emissions from seven wood combustion devices. Among total carbon mass emitted (excluding CO2), CO emissions were dominant, together with nonmethane volatile organic compounds (NMVOCs) (10-40%). Automated devices emitted 1-3 orders of magnitude lower CH4 (0.002-0.60 g kg-1 of wood) and NMVOCs (0.01-1 g kg-1 of wood) compared to batch-operated devices (CH4: 0.25-2.80 g kg-1 of wood; NMVOCs: 2.5-19 g kg-1 of wood). 60-90% of the total NMVOCs were emitted in the starting phase of batch-operated devices, except for the first load cycles. Partial-load conditions or deviations from the normal recommended operating conditions, such as use of wet wood/wheat pellets, oxygen rich or deficit conditions, significantly enhanced the emissions. NMVOCs were largely dominated by small carboxylic acids and alcohols, and furans. Despite the large variability in NMVOCs emission strengths, the relative contribution of different classes showed large similarities among different devices and combustion phases. We show that specific improper operating conditions may even for advanced technology not result in the emission reduction of secondary organic aerosol (SOA) forming compounds and thus not reduce the impact of wood combustion on climate and health.

Secondary Organic Aerosol Formation from Aromatic Alkene Ozonolysis: Influence of the Precursor Structure on Yield, Chemical Composition, and Mechanism.

The influence of the precursor chemical structure on secondary organic aerosol (SOA) formation was investigated through the study of the ozonolysis of two anthropogenic aromatic alkenes: 2-methylstyrene and indene. Experiments were carried out in three different simulation chambers: ICARE 7300L FEP Teflon chamber (ICARE, Orléans, France), EUPHORE FEP Teflon chamber (CEAM, Valencia, Spain), and CESAM evacuable stainless steel chamber (LISA, Créteil, France). For both precursors, SOA yield and growth were studied on a large range of initial concentrations (from ∼60 ppbv to 1.9 ppmv) and the chemical composition of both gaseous and particulate phases was investigated at a molecular level. Gas phase was described using FTIR spectroscopy and online gas chromatography coupled to mass spectrometry, and particulate chemical composition was analyzed (i) online by thermo-desorption coupled to chemical ionization mass spectrometry and (ii) offline by supercritical fluid extraction coupled to gas chromatography and mass spectrometry. The results obtained from a large set of experiments performed in three different chambers and using several complementary analytical techniques were in very good agreement. SOA yield was up to 10 times higher for indene ozonolysis than for 2-methylstyrene ozonolysis at the same reaction advancement. For 2-methylstyrene ozonolysis, formaldehyde and o-tolualdehyde were the two main gaseous phase products while o-toluic acid was the most abundant among six products detected within the particulate phase. For indene ozonolysis, traces of formic and phthalic acids as well as 11 species were detected in the gaseous phase and 11 other products were quantified in the particulate phase, where phthaldialdehyde was the main product. On the basis of the identified products, reaction mechanisms were proposed that highlight specific pathways due to the precursor chemical structure. These mechanisms were finally compared and discussed regarding SOA formation. In the case of 2-methylstyrene ozonolysis, ozone adds mainly on the external and monosubstituted double bond, yielding only one C8- and monofunctionalized Criegee intermediate and hence more volatile products as well as lower SOA mass than indene ozonolysis in similar experimental conditions. In the case of indene, ozone adds mainly on the five-carbon-ring and disubstituted C═C double bond, leading to the formation of two C9- and bifunctionalized Criegee intermediates, which then evolve via different pathways including the hydroperoxide channel and form highly condensable first-generation products.

Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Residential Coal Combustion.

Residential coal combustion is a significant contributor to particulate urban air pollution in Chinese mega cities and some regions in Europe. While the particulate emission factors and the chemical characteristics of the organic and inorganic aerosol from coal combustion have been extensively studied, the chemical composition and nonmethane organic gas (NMOG) emission factors from residential coal combustion are mostly unknown. We conducted 23 individual burns in a traditional Chinese stove used for heating and cooking using five different coals with Chinese origins, characterizing the NMOG emissions using a proton transfer reaction time-of-flight mass spectrometer. The measured emission factors range from 1.5 to 14.1 g/kgcoal for bituminous coals and are below 0.1 g/kgcoal for anthracite coals. The emission factors from the bituminous coals are mostly influenced by the time until the coal is fully ignited. The emissions from the bituminous coals are dominated by aromatic and oxygenated aromatic compounds with a significant contribution of hydrocarbons. The results of this study can help to improve urban air pollution modeling in China and Eastern Europe and can be used to constrain a coal burning factor in ambient gas phase positive matrix factorization studies.

Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Cooking Emissions.

Cooking processes produce gaseous and particle emissions that are potentially deleterious to human health. Using a highly controlled experimental setup involving a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), we investigate the emission factors and the detailed chemical composition of gas phase emissions from a broad variety of cooking styles and techniques. A total of 95 experiments were conducted to characterize nonmethane organic gas (NMOG) emissions from boiling, charbroiling, shallow frying, and deep frying of various vegetables and meats, as well as emissions from vegetable oils heated to different temperatures. Emissions from boiling vegetables are dominated by methanol. Significant amounts of dimethyl sulfide are emitted from cruciferous vegetables. Emissions from shallow frying, deep frying and charbroiling are dominated by aldehydes of differing relative composition depending on the oil used. We show that the emission factors of some aldehydes are particularly large which may result in considerable negative impacts on human health in indoor environments. The suitability of some of the aldehydes as tracers for the identification of cooking emissions in ambient air is discussed.

A bio-inspired analog silicon retina with Michaelis-Menten auto-adaptive pixels sensitive to small and large changes in light.

In this paper, we present: (i) a novel analog silicon retina featuring auto-adaptive pixels that obey the Michaelis-Menten law, i.e. V=V(m) I(n)/I(n)+σ(n); (ii) a method of characterizing silicon retinas, which makes it possible to accurately assess the pixels' response to transient luminous changes in a ±3-decade range, as well as changes in the initial steady-state intensity in a 7-decade range. The novel pixel, called M(2)APix, which stands for Michaelis-Menten Auto-Adaptive Pixel, can auto-adapt in a 7-decade range and responds appropriately to step changes up to ±3 decades in size without causing any saturation of the Very Large Scale Integration (VLSI) transistors. Thanks to the intrinsic properties of the Michaelis-Menten equation, the pixel output always remains within a constant limited voltage range. The range of the Analog to Digital Converter (ADC) was therefore adjusted so as to obtain a Least Significant Bit (LSB) voltage of 2.35mV and an effective resolution of about 9 bits. The results presented here show that the M(2)APix produced a quasi-linear contrast response once it had adapted to the average luminosity. Differently to what occurs in its biological counterparts, neither the sensitivity to changes in light nor the contrast response of the M(2)APix depend on the mean luminosity (i.e. the ambient lighting conditions). Lastly, a full comparison between the M(2)APix and the Delbrück auto-adaptive pixel is provided.

Physico-chemical characterization of African urban aerosols (Bamako in Mali and Dakar in Senegal) and their toxic effects in human bronchial epithelial cells: description of a worrying situation.

BACKGROUND: The involvement of particulate matter (PM) in cardiorespiratory diseases is now established in developed countries whereas in developing areas such as Africa with a high level of specific pollution, PM pollution and its effects are poorly studied. Our objective was to characterize the biological reactivity of urban African aerosols on human bronchial epithelial cells in relation to PM physico-chemical properties to identify toxic sources. METHODS: Size-speciated aerosol chemical composition was analyzed in Bamako (BK, Mali, 2 samples with one having desert dust event BK1) and Dakar (DK; Senegal) for Ultrafine UF, Fine F and Coarse C PM. PM reactivity was studied in human bronchial epithelial cells investigating six biomarkers (oxidative stress responsive genes and pro-inflammatory cytokines). RESULTS: PM mass concentrations were mainly distributed in coarse mode (60%) and were impressive in BK1 due to the desert dust event. BK2 and DK samples showed a high content of total carbon characteristic of urban areas. The DK sample had huge PAH quantities in bulk aerosol compared with BK that had more water soluble organic carbon and metals. Whatever the site, UF and F PM triggered the mRNA expression of the different biomarkers whereas coarse PM had little or no effect. The GM-CSF biomarker was the most discriminating and showed the strongest pro-inflammatory effect of BK2 PM. The analysis of gene expression signature and of their correlation with main PM compounds revealed that PM-induced responses are mainly related to organic compounds. The toxicity of African aerosols is carried by the finest PM as with Parisian aerosols, but when considering PM mass concentrations, the African population is more highly exposed to toxic particulate pollution than French population. Regarding the prevailing sources in each site, aerosol biological impacts are higher for incomplete combustion sources resulting from two-wheel vehicles and domestic fires than from diesel vehicles (Dakar). Desert dust events seem to produce fewer biological impacts than anthropogenic sources. DISCUSSION: Our study shows that combustion sources contribute to the high toxicity of F and UF PM of African urban aerosols, and underlines the importance of emission mitigation and the imperative need to evaluate and to regulate particulate pollution in Africa.

Oxidation of atmospheric humic like substances by ozone: a kinetic and structural analysis approach.

This work explores the heterogeneous reaction between HUmic-LIke Substances (so-called HULIS) and ozone. Genuine atmospheric HULIS were extracted from aerosol samples collected in Chamonix (France) in winter and used in coated flow tube experiments to evaluate heterogeneous uptake of O3 on such mixtures. The uptake coefficient (γ) was investigated as a function of pH (from 2.5 to 10), O3 concentration (from 8 to 33 × 10¹¹ molecules cm⁻³), relative humidity (20 to 65%) and photon flux (from 0 to 1.66 × 10¹5 photons cm⁻² s⁻¹). Reactive uptake was found to increase in the irradiated experiment with pH, humidity and photon flux. The extract was characterized before and after exposure to O3 and/or UV light in the attempt to elucidate the effect of the photochemical aging. Carbon content measurements, UV-vis spectroscopy and functional groups analysis revealed a decrease of the UV absorbance as well as of the carbon mass content, while the functionalization rate (COOH and C═O) and therefore the polarity increased during the simulated photochemical exposure.

Precursor ion scanning-mass spectrometry for the determination of nitro functional groups in atmospheric particulate organic matter.

An analytical method for the quantitative determination of the total nitro functional group (R-NO2) content in atmospheric particulate organic matter is developed. The method is based on the selectivity of NO2(-) (m/z 46) precursor ion scanning (PAR 46) by atmospheric pressure chemical ionization-tandem mass spectrometry (APCI-MS/MS). PAR 46 was experimented on 16 nitro compounds of different molecular structures and was compared with a neutral loss of NO (30 amu) technique in terms of sensitivity and efficiency to characterize the nitro functional groups. Covering a wider range of compounds, PAR 46 was preferred and applied to reference mixtures containing all the 16 compounds under study. Repeatability carried out using an original statistical approach, and calibration experiments were performed on the reference mixtures proven the suitability of the technique for quantitative measurements of nitro functional groups in samples of environmental interest with good accuracy. A linear range was obtained for concentrations ranging between 0.005 and 0.25 mM with a detection limit of 0.001 mM of nitro functional groups. Finally, the analytical error based on an original statistical approach applied to numerous reference mixtures was below 20%. Despite of potential artifacts related to nitro-alkanes and organonitrates, this new methodology offers a promising alternative to FT-IR measurements. The relevance of the method and its potentialities are demonstrated through its application to aerosols collected in the EUPHORE simulation chamber during o-xylene photooxidation experiments and in a suburban area of a French alpine valley during summer.

Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry.

The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF3/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L(-1). Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.

An improved biosensor for acetaldehyde determination using a bienzymatic strategy at poly(neutral red) modified carbon film electrodes.

Improved biosensors for acetaldehyde determination have been developed using a bienzymatic strategy, based on a mediator-modified carbon film electrode and co-immobilisation of NADH oxidase and aldehyde dehydrogenase. Modification of the carbon film electrode with poly(neutral red) mediator resulted in a sensitive, low-cost and reliable NADH detector. Immobilisation of the enzymes was performed using encapsulation in a sol-gel matrix or cross-linking with glutaraldehyde. The bienzymatic biosensors were characterized by studying the influence of pH, applied potential and co-factors. The sol-gel and glutaraldehyde biosensors showed a linear response up to 60 microM and 100 microM, respectively, with detection limits of 2.6 microM and 3.3 microM and sensitivities were 1.7 microA mM(-1) and 5.6 microA mM(-1). The optimised biosensors showed good stability and good selectivity and have been tested for application for the determination of acetaldehyde in natural samples such as wine.

[Defense of the nation contrary to prosperity of the discipline: military engagement and institutionalization of psychology in Canada]. / Défense de la nation contre prospérité de la discipline: engagement militaire et institutionnalisation de la psychologie au Canada.

This article contributes to our knowledge about the rise of the social and human sciences through an examination of military uses of psychology in Canada and this field sensibility to external demand. The national crisis caused by World War II and the Cold War were perceived by psychologists as sizeable opportunities to promote psychological expertise outside academe and to strengthen the social authority of their discipline and profession. By the way of military patronage and psychological contribution to National defense, psychological expertise then gained new symbolic and material resources. Does it mean that this field exogeneity undermine its disciplinary practices or knowledge production? It is said that this is an empirical question that bears no univocal answers.