Dominique Courcot

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.

Relationship between physicochemical characterization and toxicity of fine particulate matter (PM2.5) collected in Dakar city (Senegal).

The massive increase in emissions of air pollutants due to economic and industrial growth in developing countries has made air quality a crucial health problem in this continent. Hence, it is somewhat critical to have a better knowledge on the air pollution in Sub-Saharan Africa countries. Three air pollution PM2.5 samples were also collected in two urban sites (i.e., Fann and Faidherbe) in Dakar (Senegal) and in a rural site near Dakar (i.e., Ngaparu). The two urban sites mainly differ in the type of used vehicles: in Fann, most of the traffic is made of buses, which are absent, in Faidherbe. The physicochemical characteristics of the three PM2.5 samples revealed their high heterogeneities and complexities, related to the multiple natural and anthropogenic emission sources. Results from 5-bromodeoxyuridine incorporation into DNA, mitochondrial dehydrogenase activity, and extracellular lactate dehydrogenase activity in PM2.5-exposed BEAS-2B cells suggested the exposure conditions (i.e., 3 and 12 μg PM/cm² during 24, 48, and 72 h) to further consider. The organic fractions (i.e., mainly PAHs) of the PM(2.5) samples were able to induce a time and/or concentration-dependent gene expression of CYP1A1 and CYP1B1, and, to a lesser extent, NQO1. There was a time and/or dose-dependent increase of both the gene expression and/or protein secretion of inflammatory mediators (i.e., TNF-α, IL-1β, IL-6, and/or IL-8) in PM(2.5)-exposed BEAS-2B cells. In agreement with the physicochemical characterization, urban PM(2.5) samples caused greater biological responses in BEAS-2B cells than the rural one. Variable concentrations of transition metals (i.e., Fe, Al, Pb, Mn, Zn) and organic compounds (i.e., PAHs) founded in the three PM2.5 samples might be firmly involved in a time- and/or dose-dependent toxicity, relying on inflammatory processes.

Effect of potassium on the surface potential of titania

The surface potential, χ, of several commercial titania powders has been measured by the vibrating condenser method in the temperature range 100–450 °C in air. The K impurity detected by XPS on some of titanias lowers the χ value of TiO2 considerably. A series of K-doped TiO2 anatase samples containing from 1.1 to 11 K atoms nm–2 was prepared and examined by surface potential and XPS techniques. The surface potential of anatase decreases linearly with increasing potassium content up to ca. 2.4 K atoms nm–2, and then remains constant. The surface potential of K-doped samples varies to a smaller extent with temperature compared with undoped anatase. On the basis of the surface potential and XPS data obtained, it is suggested that the mode of K deposition on the surface of anatase changes at a coverage of about 2 K atoms nm–2.

Temporal-spatial variations of the physicochemical characteristics of air pollution Particulate Matter (PM2.5-0.3) and toxicological effects in human bronchial epithelial cells (BEAS-2B).

While the evidence for the health adverse effects of air pollution Particulate Matter (PM) has been growing, there is still uncertainty as to which constituents within PM are most harmful. Hence, to contribute to fulfill this gap of knowledge, some physicochemical characteristics and toxicological endpoints (i.e. cytotoxicity, oxidative damage, cytokine secretion) of PM2.5-0.3 samples produced during two different seasons (i.e. spring/summer or autumn/winter) in three different surroundings (i.e. rural, urban, or industrial) were studied, thereby expecting to differentiate their respective adverse effects in human bronchial epithelial cells (BEAS-2B). Physicochemical characteristics were closely related to respective origins and seasons of the six PM2.5-0.3 samples, highlighting the respective contributions of industrial and heavy motor vehicle traffic sources. Space- and season-dependent differences in cytotoxicity of the six PM2.5-0.3 samples could only be supported by considering both the physicochemical properties and the variance in air PM concentrations. Whatever spaces and seasons, dose- and even time-dependent increases in oxidative damage and cytokine secretion were reported in PM2.5-0.3-exposed BEAS-2B cells. However, the relationship between the chemical composition of each of the six PM2.5-0.3 samples and their oxidative or inflammatory potentials seemed to be very complex. These results supported the role of inorganic, ionic and organic components as exogenous source of Reactive Oxygen Species and, thereafter, cytokine secretion. Nevertheless, one of the most striking observation was that some inorganic, ionic and organic chemical components were preferentially associated with early oxidative events whereas others in the later oxidative damage and/or cytokine secretion. Taken together, these results indicated that PM mass concentration alone might not be able to explain the health outcomes, because PM is chemically nonspecific, and supported growing evidence that PM-size, composition and emission source, together with sampling season, interact in a complex manner to produce PM2.5-0.3-induced human adverse health effects.

Effect of the sequence of potassium introduction to V2O5/TiO2 catalysts on their physicochemical properties and catalytic performance in oxidative dehydrogenation of propane

Abstract Two series of K-promoted V 2 O 5 /TiO 2 catalysts were prepared by: (a) deposition of vanadia on K-doped TiO 2 support (TiK V preparations), and (b) deposition of K on vanadia-titania catalysts (TiV K preparation). They were characterized by 51 V NMR, XPS, surface potential (work function) techniques and isopropanol decomposition, a probe reaction for the acid-base properties, and tested in oxidative dehydrogenation of propane (ODH). It has been found that the sequence of the K introduction in the preparation step is preserved in the calcined preparations, with more potassium being present on the surface of TiV K than TiK V catalysts. The vanadium species on TiK V samples include V 2 O 5 and polymeric [VO x ] γ species. The TiV K sequence leads to the formation of potassium vanadates (KV 3 O 8 and possibly KVO 3 ), and to the decrease in the amount of V 2 O 5 . The TiV K catalysts are more active and selective in the ODH of propane, and more active in isopropanol dehydrogenation to the acetone (thus more basic) than the TiK V samples.

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.

Mutagenicity and clastogenicity of native airborne particulate matter samples collected under industrial, urban or rural influence

Airborne particulate matter has recently been classified by the IARC as carcinogenic to humans (group 1). However, the link between PM chemical composition and its carcinogenicity is still unclear. The aim of the present study was to evaluate and to compare genotoxic potencies of 6 native PM samples collected in spring-summer or autumn-winter, either in industrial, urban or rural area. We evaluated their mutagenicity through Ames test on YG1041, TA98, and TA102 tester strains, and their clastogenicity on human bronchial epithelial BEAS-2B cells using comet assay, γ-H2AX quantification, and micronucleus assay. Ames test results showed a strong positive response, presumably associated with nitro-aromatics content. In addition, at least 2 positive responses were observed out of the 3 genotoxicity assays for each of the 6 samples, demonstrating their clastogenicity. Our data suggest that PM samples collected in autumn-winter season are more genotoxic than those collected in spring-summer, potentially because of higher concentrations of adsorbed organic compounds. Taken together, our results showed the mutagenicity and clastogenicity of native PM₂.₅ samples from different origins, and bring additional elements to explain the newly recognized carcinogenicity of outdoor air pollution.

Effect of potassium addition to the TiO2 support on the structure of V2O5/TiO2 and its catalytic properties in the oxidative dehydrogenation of propane

Vanadium oxide has been deposited by a grafting technique onto TiO2 anatase, both pure and doped with potassium [(1.2 and 2.5) atoms nm–2]. The V content varied between 0.1 and 20 atoms nm–2[0.01–2 V2O5 monolayers (ML)]. The prepared samples were characterized by X-ray photoelectron spectroscopy (XPS), 51V magic-angle spinning (MAS) NMR and a surface potential (SP) technique and tested as catalysts in the oxidative dehydrogenation (ODH) of propane and propan-2-ol decomposition, a probe reaction for acid–base properties. From the XPS and SP data it has been inferred that VOx are located beside the K centres on the bare surface of TiO2 with the lower K content sample, whereas they cover the K-doped fraction of the surface for the sample with higher K content. Monomeric and polymeric VOx species and V2O5 were detected by 51V NMR on pure and K-doped catalysts. For the K-doped samples the polymeric species were observed only at high V content and new tetrahedral VOx species and traces of KVO3 appeared. It has been found that the presence of K on the TiO2 surface leads to (a) a decrease in the reducibility of the vanadia phase at low V content; (b) a decrease in the surface potential (electronic work function); (c) a decrease in acidity and increase in basicity and (d) a decrease in the total activity for ODH of propane. The pattern of the activity and selectivity changes with the total V content depends on the amount of K on the support surface: with K 1 ML) are required to obtain the same catalytic performance. Polymeric [VOx] species seem to be more active and selective in the ODH of propane than monomeric species or bulk V2O5.

Effects of environmental cadmium and lead exposure on adults neighboring a discharge: Evidences of adverse health effects

The purpose of the study was to determine Pb and Cd concentrations in humans and to assess the effect of co-exposure to these metals on biomarkers of oxidative stress and nephrotoxicity. Blood and urine levels of Pb and Cd, oxidative stress and urinary renal biomarkers were measured in 77 subjects neighboring a discharge and 52 in the control site. Exposed subjects showed significantly higher levels of lead and cadmium in blood and urine than the controls. Excessive production of reactive oxygen species induced by these metals in exposed subjects conducted to a decrease in antioxidant defense system (GPx, Selenium, GSH) and an increase in lipid peroxidation (MDA). Moreover, changes in markers of nephrotoxicity (high urinary concentrations of total protein, RBP and CC16, as well as GSTα and LDH increased activities) suggested the occurrence of discrete and early signs of impaired renal function for the discharge neighboring population.

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.