Frédéric Ledoux

Chemical profile identification of fugitive and confined particle emissions from an integrated iron and steelmaking plant

The aim of this study is to obtain the characteristic inorganic chemical profile of important particle sources identified in the integrated iron and steel process: sintering, blast furnace, steelmaking and desulfurization slag processing. A complete chemical and physical characterization program was developed: particle size distribution, chemical analysis, XRD, SEM-EDX and TGA/DTA. The sample collected from the sinter stack showed high levels of K and Cl(-), followed by Fe, NH4(+), Ca, Na and Pb. The profile of the dust samples taken from the sinter cake discharge zone was quite different, showing higher amounts of Fe, Ca and Al, and lower amounts of K, Cl(-), Na and Pb. Dust samples collected from the blast furnace (BF) and steelmaking cast house may be distinguished from each other based on the higher levels of Fe (hematite and magnetite) and lower levels of Ca, Zn and C (graphite) found in BF dust. High levels of Ca and Fe were found in samples taken from the desulfurization slag processing area. Such information can be useful for source apportionment studies at receptor sites that could be influenced by iron and steelmaking plant emissions.

Genotoxic and epigenotoxic effects of fine particulate matter from rural and urban sites in Lebanon on human bronchial epithelial cells

Assessment of air pollution by particulate matter (PM) is strongly required in Lebanon in the absence of an air quality law including updated air quality standards. Using two different PM2.5-0.3 samples collected at an urban and a rural site, we examined genotoxic/epigenotoxic effects of PM exposure within a human bronchial epithelial cell line (BEAS-2B). Inorganic and organic contents evidence the major contribution of traffic and generating sets in the PM2.5-0.3 composition. Urban PM2.5-0.3 sample increased the phosphorylation of H2AX, the telomerase activity and the miR-21 up-regulation in BEAS-2B cells in a dose-dependent manner. Furthermore, urban PM2.5-0.3 induced a significant increase in CYP1A1, CYP1B1 and AhRR genes expression. The variable concentrations of transition metals and organic compounds detected in the collected PM2.5-0.3 samples might be the active agents leading to a cumulative DNA damage, critical for carcinogenesis.

Traffic-related air pollution. A pilot exposure assessment in Beirut, Lebanon

Traffic-related volatile organic compounds (VOCs) pollution has frequently been demonstrated to be a serious problem in the developing countries. Benzene and 1,3-butadiene (BD) have been classified as a human carcinogen based on evidence for an increased genotoxic and epigenotoxic effects in both occupational exposure assessment and in vivo/in vitro studies. We have undertaken a biomonitoring of 25 traffic policemen and 23 office policemen in Beirut, through personal air monitoring, assessed by diffusive samplers, as well as through the use of biomarkers of exposure to benzene and BD. Personal benzene, toluene, ethylbenzene, and xylene (BTEX) exposure were quantified by GC-MS/MS, urinary trans, trans-muconic acid (t,t-MA) by HPLC/UV, S-phenyl mercapturic acid (S-PMA), monohydroxy-butenyl mercapturic acid (MHBMA) and dihydroxybutyl mercapturic acid (DHBMA) by ultra-performance liquid chromatography-electrospray tandem mass spectrometry (UPLC/ESI(-)-MS/MS) in MRM (Multiple Reaction Monitoring) mode. We found that individual exposure to benzene in the traffic policemen was higher than that measured in traffic policemen in Prague, in Bologna, in Ioannina and in Bangkok. t,t-MA levels could distinguish between office and traffic policemen. However, median MHBMA levels in traffic policemen were slightly elevated, though not significantly higher than in office policemen. Alternatively, DHBMA concentrations could significantly distinguish between office and traffic policemen and showed a better correlation with personal total BTEX exposure. DHMBA, measured in the post-shift urine samples, correlated with both pre-shift MHMBA and pre-shift DHMBA. Moreover, there was not a marked effect of smoking habits on DHBMA. Taken together, these findings suggested that DHBMA is more suitable than MHBMA as biomarker of exposure to BD in humans. Traffic policemen, who are exposed to benzene and BD at the roadside in central Beirut, are potentially at a higher risk for development of diseases such as cancer than office policemen.

PM2.5 source apportionment in a French urban coastal site under steelworks emission influences using constrained non-negative matrix factorization receptor model

The constrained weighted-non-negative matrix factorization (CW-NMF) hybrid receptor model was applied to study the influence of steelmaking activities on PM2.5 (particulate matter with equivalent aerodynamic diameter less than 2.5 μm) composition in Dunkerque, Northern France. Semi-diurnal PM2.5 samples were collected using a high volume sampler in winter 2010 and spring 2011 and were analyzed for trace metals, water-soluble ions, and total carbon using inductively coupled plasma--atomic emission spectrometry (ICP-AES), ICP--mass spectrometry (ICP-MS), ionic chromatography and micro elemental carbon analyzer. The elemental composition shows that NO3(-), SO4(2-), NH4(+) and total carbon are the main PM2.5 constituents. Trace metals data were interpreted using concentration roses and both influences of integrated steelworks and electric steel plant were evidenced. The distinction between the two sources is made possible by the use Zn/Fe and Zn/Mn diagnostic ratios. Moreover Rb/Cr, Pb/Cr and Cu/Cd combination ratio are proposed to distinguish the ISW-sintering stack from the ISW-fugitive emissions. The a priori knowledge on the influencing source was introduced in the CW-NMF to guide the calculation. Eleven source profiles with various contributions were identified: 8 are characteristics of coastal urban background site profiles and 3 are related to the steelmaking activities. Between them, secondary nitrates, secondary sulfates and combustion profiles give the highest contributions and account for 93% of the PM2.5 concentration. The steelwork facilities contribute in about 2% of the total PM2.5 concentration and appear to be the main source of Cr, Cu, Fe, Mn, Zn.

Characterisation and seasonal variations of particles in the atmosphere of rural, urban and industrial areas: Organic compounds

Atmospheric aerosol samples (PM2.5-0.3, i.e., atmospheric particles ranging from 0.3 to 2.5μm) were collected during two periods: spring-summer 2008 and autumn-winter 2008-2009, using high volume samplers equipped with cascade impactors. Two sites located in the Northern France were compared in this study: a highly industrialised city (Dunkirk) and a rural site (Rubrouck). Physicochemical analysis of particulate matter (PM) was undertaken to propose parameters that could be used to distinguish the various sources and to exhibit seasonal variations but also to provide knowledge of chemical element composition for the interpretation of future toxicological studies. The study showed that PM2.5-0.3 concentration in the atmosphere of the rural area remains stable along the year and was significantly lower than in the urban or industrial ones, for which concentrations increase during winter. High concentrations of polycyclic aromatic hydrocarbons (PAHs), dioxins, furans and dioxin like polychlorinated biphenyls (DL-PCBs), generated by industrial activities, traffic and municipal wastes incineration were detected in the samples. Specific criteria like Carbon Preference Index (CPI) and Combustion PAHs/Total PAHs ratio (CPAHs/TPAHs) were used to identify the possible sources of atmospheric pollution. They revealed that paraffins are mainly emitted by biogenic sources in spring-summer whereas as in the case of PAHs, they have numerous anthropogenic emission sources in autumn-winter (mainly from traffic and domestic heating).

EPR investigations of Mn2+, Fe3+ ions and carbonaceous radicals in atmospheric particulate aerosols during their transport over the eastern coast of the English Channel

Abstract Electron paramagnetic resonance (EPR) spectroscopy was used to follow the evolution of the chemical forms of manganese and study other paramagnetic species in the atmospheric particulate aerosols at Wimereux, a French station located on the eastern coast of the English Channel. In parallel, Graphite Furnace Atomic Absorption Spectrometry (GFAAS) was used to measure the metal concentrations. Fe concentration values are common in North Sea sites, but those of Mn are quite higher due to the presence of an important local source of Mn. EPR spectra have evidenced isolated Fe3+ and Mn2+ ions and carbonaceous products with variable intensities according to the wind directions. Amounts of paramagnetic species and carbonaceous products are maximum for continental winds and minimum for marine winds. Three Mn types were identified depending on the sampling distance from the source of emission and the size of the particles.

Comparison between ultrafine and fine particulate matter collected in Lebanon: Chemical characterization, in vitro cytotoxic effects and metabolizing enzymes gene expression in human bronchial epithelial cells

During the last few years, the induction of toxicological mechanisms by atmospheric ultrafine particles (UFP) has become one of the most studied topics in toxicology and a subject of huge debates. Fine particles (FP) and UFP collected at urban and rural sites in Lebanon were studied for their chemical composition and toxicological effects. UFP were found more enriched in trace elements, secondary inorganic ions, total carbon and organic compounds than FP. For toxicological analysis, BEAS-2B cells were exposed for 24, 48 and 72 h to increasing concentrations of FP, water-UFP suspension (UFPw) and UFP organic extract (UFPorg). Our findings showed that UFP caused earlier alterations of mitochondrial metabolism and membrane integrity from the lowest concentrations. Moreover, a significant induction of CYP1A1, CYP1B1 and AhRR genes expression was showed after cells exposure to UFPorg and to a lesser extent to UFPw and FP samples.

Atmospheric aerosols behaviour at an industrial area in Northern France

Aerosols samplings by bulk filtration and by use of a high volume cascade impactor were performed taking into account wind directions simultaneously at an urban and a rural site in Northern France. Fifteen major and trace species were considered to study characteristics of the particles collected. Evolution of the Weighted Mean Diameter vs. the wind direction, profiles of the Mass Size Function (MSF), values of the dry deposition fluxes, distribution between the coarse particles (>1 μm) and the fine particles (<1 μm), neutralisation ratio between NH4+ and SO42−, NO3− are discussed in this work.

Physicochemical characteristics, mutagenicity and genotoxicity of airborne particles under industrial and rural influences in Northern Lebanon

In this work, the main objectives were to assess the mutagenic and genotoxic effects of fine particulate matter collected in an industrial influenced site in comparison with a non-industrial influenced one (rural site) and to relate the particulate matter (PM) composition to the observed genotoxic effects. At the industrial influenced site, higher concentrations of phosphates, trace metals, and polycyclic aromatic hydrocarbons (PAHs) in particles could be related to the contributions of quarries, fertilizer producer, cement plants, and tires burning. Gasoline and diesel combustion contributions were evidenced in particles collected at both sites. Particles collected under industrial influence showed a higher mutagenic potential on three tested strains of Salmonella typhimurium (TA98, YG1041, and TA102), and especially on the YG1041, compared to particles from the rural site. Furthermore, only particles collected in the vicinity of the industrial site showed a tendency to activate the SOS responses in Escherichia coli PQ37, which is indicative of DNA damage as a result of exposure of the bacteria cells to the action of mutagenic samples. The mutagenicity and genotoxicity of the industrial PM2.5–0.3 particulates may be attributed to its composition especially in organic compounds. This study showed that proximity of industries can affect local PM composition as well as PM genotoxic and mutagenic potential.

The Use of a Non Negative Matrix Factorization Method Combined to PM2.5 Chemical Data for a Source Apportionment Study in Different Environments

This study revolves around the use of a Non Negative Matrix Factorization method under constraints for the identification sources profiles as well as their respective contributions in three sites in northern France. Using PM2.5 chemical analysis data, the model identified eight background and four local industrial sources profiles. In addition, the contributions of these profiles showed that secondary aerosols and combustion sources are the major constituents of the analyzed PM2.5, whereas industrial contributions were found majorly responsible for the elemental enrichments.