Incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS)-based strategy for direct measurement of aerosol extinction in a lidar blind zone.

In this Letter, the development of a custom-designed incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) and its application to in situ measurement of aerosol extinction near the ground surface are described in an effort to address the issue of missing data in the light detection and ranging (lidar) blind zone in the first hundreds of meters of the observation range. Combined measurements of aerosol extinction at the same location using lidar remote sensing at 355 nm and in situ IBBCEAS operating in the UV spectral region around 370 nm showed results with a good correlation (${{\rm R}^2} = {0.90}$R2=0.90) between the two measurement techniques. This Letter highlights a new strategy for near-end lidar calibration, using a ground-based compact and robust IBBCEAS located at the lidar measurement site to determine the vertical profile of the aerosol extinction coefficient with a higher accuracy.

A Quantum Cascade Laser-Based Optical Sensor for Continuous Monitoring of Environmental Methane in Dunkirk (France).

A room-temperature continuous-wave (CW) quantum cascade laser (QCL)-based methane (CH4) sensor operating in the mid-infrared near 8 µm was developed for continuous measurement of CH4 concentrations in ambient air. The well-isolated absorption line (7F2,4 ← 8F1,2) of the ν4 fundamental band of CH4 located at 1255.0004 cm(-1) was used for optical measurement of CH4 concentration by direct absorption in a White-type multipass cell with an effective path-length of 175 m. A 1σ (SNR = 1) detection limit of 33.3 ppb in 218 s was achieved with a measurement precision of 1.13%. The developed sensor was deployed in a campaign of measurements of time series CH4 concentration on a site near a suburban traffic road in Dunkirk (France) from 9th to 22nd January 2013. An episode of high CH4 concentration of up to ~3 ppm has been observed and analyzed with the help of meteorological parameters combined with back trajectory calculation using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model of NOAA.

Physical and chemical characteristics of particles emitted by a passenger vehicle at the tire-road contact.

Non-exhaust emissions are now recognized as a significant source of atmospheric particulate matter and the trend towards a reduction of conventionally fueled internal combustion engine vehicles on the road is increasing their contribution to air pollution due to lower exhaust emissions. These particles include brake wear particles (BWP) and tire-road contact particles (TRCP), which are composed of tire wear particles (TWP), road wear particles (RWP) and resuspended road dust (RRD). The goal of this study has therefore been to design an original experimental approach to provide insight into the chemical composition of particles emitted at the tire-road contact, focusing on the micron (PM10-1µm) and submicron (PM1-0.1µm) fractions. Through this characterization, an examination of the different TRCP generated by different materials (tire, road surface, brake system) was conducted. To achieve this, TRCP were collected at the rear of the wheel of an instrumented vehicle during road and track tests, and a SEM-EDX analysis was performed. Our experimental conditions have allowed us to demonstrate that, at the individual particle scale, TRCP are consistently associated with road dust materials and particles solely composed of tire or road materials are practically non-existent. The contribution of BWP to TRCP is marked by the emission of Fe-rich particles, including heavy metals like Ba, Mn and Cr. TWP, which result from rubber abrasion, consist of C-rich particles abundant in Si, Zn, and S. RWP, mainly composed of Al, Si, Fe, and Ca, can be either part of RRD or internally mixed with emitted TWP. The findings of this study highlight the substantial role of RRD to TRCP emissions under real driving conditions. Consequently, it underscores the importance of examining them simultaneously to achieve a more accurate estimation of on-road traffic emissions beyond the vehicle exhaust.

Sorption of 4-n-nonylphenol, 4-n-octylphenol, and 4-tert-octyphenol on cyclodextrin polymers.

Alkylphenols are industrial pollutants commonly present in wastewater. They are difficult to eliminate by conventional treatment processes, ending up in the sludge of wastewater treatment plants. In this study, we propose to use cross-linked cyclodextrin-based polymers (ECP) as sorbents to treat three alkylphenols, namely, one nonylphenol (4-n-NP) and two octylphenols (4-n-OP and 4-tert-OP), present in aqueous solution by a batch method. The experiments were carried out with five cyclodextrin polymers (α-ECP, ß-ECP, γ-ECP, α,ß,γ-ECP, and HP-ß-ECP). Sorption results showed that all polymers, with the exception of α-ECP, had high sorption capacities between 60 and 100% of the alkylphenols in the concentration range studied (between 25 and 100 µg/L). In all cases, HP-ß-ECP has shown the highest removals, regardless of the structure of the molecule. The order obtained was HP-ß-ECP >> ß-ECP ~ α,ß,γ-ECP >> γ-ECP > α-ECP. The 4-tert-OP compound was the best adsorbed, regardless the material and the solution studied. Sorption results also indicated that (i) the sorption efficiency decreased with the increasing of alkylphenol concentration; (ii) sodium chloride had a strong negative effect on the sorption process; and (iii) the performance remained unchanged after five sorption-regeneration cycles. The main sorption mechanism of alkylphenols occurring in ECP was the inclusion within the cyclodextrin cavities. The obtained results proved that cyclodextrin polymers could serve as efficient sorbents for the removal of alkylphenols from real effluents.

Investigation on the near-field evolution of industrial plumes from metalworking activities.

In a context where a significant fraction of the population lives near industrial areas, the main objectives of this study are to provide (a) new data on PM2.5 chemical compositions, heavy-metal concentrations and trace gases released by metalworking activities and (b) new information on the near-field evolution (up to about a thousand meters) of such industrial plumes in terms of particle chemical composition and size distribution. For that purpose, a one-month field campaign was performed in an industrial area near the city of Dunkirk (Northern France), combining measurements of atmospheric dynamics and physico-chemical characterization of air masses. Comparisons between several elemental ratios (mainly Mn/Fe), particle size distributions and volatile organic compound (VOC) concentrations at the stacks and at a near-field site suggest that plumes of a ferromanganese alloy plant were quickly mixed with pollutants emitted by other sources (mainly other industries, possibly traffic and sea spray), in particular a neighboring steelworks, before reaching the sampling site. This led to the emergence of secondary particles related to condensation and/or aggregation phenomena inside the plumes. Metalworking emissions were also identified as a source of new particle formation, formed through the emission of gaseous precursors and their fast transformation and condensation, over a timescale of minutes before reaching the near-field site 800 m downwind. Ultrafine particles emitted at the stacks also quickly agglomerated to form larger particles before reaching the near-field site. These results show that, even over short distances, the chemical composition and size distribution of metalworking plumes may evolve rapidly and the characteristics of particles at the boundary of an industrial area (especially in contiguous urban areas) may differ from those emitted directly at the stacks.

Characterization of smoke and dust episode over West Africa: comparison of MERRA-2 modeling with multiwavelength Mie-Raman lidar observations.

Observations of multiwavelength Mie-Raman lidar taken during the SHADOW field campaign are used to analyze a smoke-dust episode over West Africa on 24-27 December 2015. For the case considered, the dust layer extended from the ground up to approximately 2000 m while the elevated smoke layer occurred in the 2500-4000 m range. The profiles of lidar measured backscattering, extinction coefficients, and depolarization ratios are compared with the vertical distribution of aerosol parameters provided by the Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2). The MERRA-2 model simulated the correct location of the near-surface dust and elevated smoke layers. The values of modeled and observed aerosol extinction coefficients at both 355 and 532 nm are also rather close. In particular, for the episode reported, the mean value of difference between the measured and modeled extinction coefficients at 355 nm is 0.01 km-1 with SD of 0.042 km-1. The model predicts significant concentration of dust particles inside the elevated smoke layer, which is supported by an increased depolarization ratio of 15 % observed in the center of this layer. The modeled at 355 nm the lidar ratio of 65 sr in the near-surface dust layer is close to the observed value (70 ± 10) sr. At 532 nm, however, the simulated lidar ratio (about 40 sr) is lower than measurements (55 ± 8 sr). The results presented demonstrate that the lidar and model data are complimentary and the synergy of observations and models is a key to improve the aerosols characterization.

Simultaneous removal of five triazole fungicides from synthetic solutions on activated carbons and cyclodextrin-based adsorbents.

In this study, an adsorption-oriented process for the removal of fungicides from polycontaminated aqueous solutions was applied. To remove triazole fungicides from aqueous mixtures of propiconazole (PROPI), tebuconazole (TEBU), epoxiconazole (EPOXI), bromuconazole (BROMU) and difenoconazole (DIFENO), several materials used as adsorbents were compared using batch experiments, namely two conventional activated carbons (ACs) and five nonconventional cross-linked cyclodextrin (CD)-based materials (α-CDP, ß-CDP, γ-CDP, αßγ-CDP mixture, and hydroxypropyl-ß-CDP). This article presents the abatements obtained. As expected, ACs exhibited the highest levels of triazole fungicide removal: the treatment lowered the five azoles by more than 99%, and adsorption was non-selective. Concerning CD-based materials employed for the first time for the removal of fungicides from polycontaminated aqueous solutions, results were interesting in particular for hydroxypropyl-ß-CDP: 1 g of adsorbent placed in 1 L of solution containing 1 mg of each of five triazoles (5 mg in total) was able to remove over half of the fungicide amount (2.97 mg). The order obtained was the following: BROMU << PROPI ≅ EPOXI < TEBU << DIFENO. This indicates that, in the mixture studied, strong competition prevailed among fungicides for the binding sites.

Efficient degradation of phenol using natural clay as heterogeneous Fenton-like catalyst.

A natural containing Fe-clay (NRC) was used for the Fenton-like oxidation of phenol. This new catalyst was very efficient in phenol elimination in aqueous medium under mild experimental conditions (20 °C, atmospheric pressure and low concentration of hydrogen peroxide). The influence of different parameters like calcination's temperature, particle size, initial phenol and H2O2 concentrations were examined considering both phenol conversion and total organic carbon (TOC) removal. NRC was characterized by several complementary methods including chemical analysis, X-ray diffraction (XRD), Mössbauer spectroscopy, thermogravimetry-differential thermal analysis (TG-DTA), temperature programmed reduction (TPR) and BET. The experimental results showed that 100 % phenol conversion and 70 % TOC removal can be achieved using sieved and calcined NRC (d < 50 µm/450 °C). Catalytic activity of NRC was mainly attributed to the amount of iron oxide species (12.15 wt.%) present naturally in the clay.

Development of a methodology examining the behaviours of VOCs source apportionment with micro-meteorology analysis in an urban and industrial area.

During summer 2009, online measurements of 25 Volatile Organic Compounds (VOCs) from C6 to C10 as well as micro-meteorological parameters were simultaneously performed in the industrial city of Dunkerque. With the obtained data set, we developed a methodology to examine how the contributions of different source categories depend on atmospheric turbulences, and the results provided identification of emission modes. Eight factors were resolved by using Positive Matrix Factorization model and three of them were associated with mixed sources. The observed behaviours of contributions with turbulences lead to attribute some factors with sources at ground level, and some other factors with sources in the upper part of surface layer. The impact of vertical turbulence on the pollutant dispersion is also affected by the distance between sources and receptor site.

Fast changes in chemical composition and size distribution of fine particles during the near-field transport of industrial plumes.

Aerosol sampling was performed inside the chimneys and in the close environment of a FeMn alloys manufacturing plant. The number size distributions show a higher abundance of ultrafine aerosols (10-100 nm) inside the plume than upwind of the plant, indicating the emissions of nanoparticles by the industrial process. Individual analysis of particles collected inside the plume shows a high proportion of metal bearing particles (Mn-/Fe-) consisting essentially of internally mixed aluminosilicate and metallic compounds. These particles evolve rapidly (in a few minutes) after emission by adsorption of VOC gas and sulfuric acid emitted by the plant but also by agglomeration with pre-existing particles. At the moment, municipalities require a monitoring of industrial emissions inside the chimneys from manufacturers. However those measures are insufficient to report such rapid changes in chemical composition and thus to evaluate the real impact of industrial plumes in the close environment of plants (when those particles leave the industrial site). Consequently, environmental authorities will have to consider such fast evolutions and then to adapt future regulations on air pollution sources.