Bioaccessibility of trace elements in fine and ultrafine atmospheric particles in an industrial environment.

The lung bioaccessibility, i.e., the solubility in alveolar lung fluid of metals in particulate matter, has been recognized as an important parameter for health risk assessment, associated with the inhalation of airborne particles. The purpose of this study is to use an in vitro method to estimate the pulmonary bioaccessibility of toxic metals in different particle sizes, from a multi-influenced industrial emission area. The fine and ultrafine particles collected with cascade impactors in the chimneys and at different distances from a Fe-Mn smelter were extracted with a simulated alveolar fluid (Gamble solution). In addition, a four-step sequential extraction procedure was employed to approach the metal speciation. The bioaccessibility of metals ranged from almost insoluble for Fe (<1%) to extremely soluble for Rb (>80%). In terms of particle size, the trace element bioaccessibility is generally higher for the finer size fractions (submicron and ultrafine particles) than for the coarse one (>1 µm). These submicron particles have a very high number concentration and specific surface area, which confer them an important contact surface with the alveolar fluid, i.e., a higher bioaccessibility. Interestingly, the bioaccessibility of most metals clearly increases between the chimney stacks and the close environment of the studied Fe-Mn smelter, over a very short distance (800 m), possibly due to a mix with surrounding steelworks emissions. This increase is not observed over a greater distance from the smelter (2000 m), when industrial particles were mixed with urban aerosols, except for Fe, under more soluble forms in combustion particles.

Different approaches to explore the impact of COVID-19 lockdowns on carbonaceous aerosols at a European rural background site.

To prevent the fast spread of COVID-19, worldwide restrictions have been put in place, leading to a reduction in emissions from most anthropogenic sources. In this study, the impact of COVID-19 lockdowns on elemental (EC) and organic (OC) carbon was explored at a European rural background site combining different approaches: - "Horizontal approach (HA)" consists of comparing concentrations of pollutants measured at 4 m a.g.l. during pre-COVID period (2017-2019) to those measured during COVID period (2020-2021); - "Vertical approach (VA)" consists of inspecting the relationship between OC and EC measured at 4 m and those on top (230 m) of a 250 m-tall tower in Czech Republic. The HA showed that the lockdowns did not systematically result in lower concentrations of both carbonaceous fractions unlike NO2 (25 to 36 % lower) and SO2 (10 to 45 % lower). EC was generally lower during the lockdowns (up to 35 %), likely attributed to the traffic restrictions whereas increased OC (up to 50 %) could be attributed to enhanced emissions from the domestic heating and biomass burning during this stay-home period, but also to the enhanced concentration of SOC (up to 98 %). EC and OC were generally higher at 4 m suggesting a greater influence of local sources near the surface. Interestingly, the VA revealed a significantly enhanced correlation between EC and OC measured at 4 m and those at 230 m (R values up to 0.88 and 0.70 during lockdown 1 and 2, respectively), suggesting a stronger influence of aged and long distance transported aerosols during the lockdowns. This study reveals that lockdowns did not necessarily affect aerosol absolute concentrations but it certainly influenced their vertical distribution. Therefore, analyzing the vertical distribution can allow a better characterization of aerosol properties and sources at rural background sites, especially during a period of significantly reduced human activities.

Mass absorption cross-section and absorption enhancement from long term black and elemental carbon measurements: A rural background station in Central Europe.

Black carbon (BC) is a dominant aerosol light absorber, and its brown carbon (BrC) coating can enhance absorption and lead to uncertainties concerning the radiative forcing estimation. This study investigates the mass absorption cross-section of equivalent BC (MACeBC) during a long-term field measurement (2013-2017) at a rural Central European site. The MAC enhancement factor (Eabs) and the contribution of BrC coatings to the absorption coefficient (Babs) were estimated by combining different approaches. The annual mean Babs and MACeBC values decreased slightly over the measurement period associated with change in the submicron aerosol size distribution. Regardless of the wavelength, Babs exhibited clear seasonal and diurnal variations, with higher values in winter when a higher absorption Ångström exponent (1.4) was observed due to the local biomass burning (BB). In contrast, MACeBC did not have a distinct temporal trend at 600 nm (7.84 ± 2.79 m2 g-1), while it showed a seasonal trend at 370 nm with higher values in winter (15.64 ± 4.77 m2 g-1). During this season, Eabs_660 was 1.18 ± 0.27 and did not exhibit any clear wavelength dependence, despite the influence of BB. During the study period, BrC-attributed absorption was observed in 31% of the samples, with a contribution of up to 40% of total Babs. In summer, the Eabs_660 increased to 1.59 ± 0.60, when a larger BC coating could be formed by secondary aerosol fractions. During this season, MACeBC_660 and Eabs_660 showed comparable source profiles that were mainly associated with aged air masses over central Europe, thereby supporting the fact that characteristics of coating materials formed during atmospheric aging are a major factor driving the MACeBC_660 measured at the regional background site. Further field investigations of the composition of BC coatings would help to better understand and estimate uncertainties related to the radiative effect of aerosols.

Characterization and source apportionment of single particles from metalworking activities.

Industrial metalworking facilities emit a variety of air toxics including volatile organic compounds, polycyclic aromatic hydrocarbons (PAHs) and heavy metals. In order to investigate these emissions, a 1-month multi-instrument field campaign was undertaken at an industrial site in Grande-Synthe, Dunkirk (France), in May and June 2012. One of the main objectives of the study was to provide new information on the chemical composition of particulate matter with aerodynamic diameters smaller than 2.5 µm (PM2.5) in the vicinity of metalworking facilities. An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed to provide size-resolved chemical mixing state measurements of ambient single particles at high temporal resolution. This mixing state information was then used to apportion PM2.5 to local metalworking facilities influencing the receptor site. Periods when the site was influenced by metalworking sources were characterised by a pronounced increase in particles containing toxic metals (manganese, iron, lead) and polycyclic aromatic hydrocarbons (PAHs) with a variety of chemical mixing states. The association of specific particle classes with a nearby ferromanganese alloy manufacturing plant was confirmed through comparison with previous analysis of raw materials (ores) and chimney filter particle samples collected at the facility. Particles associated with emissions from a nearby steelworks were also identified. The contribution of local metalworking activities to PM2.5 at the receptor site for the period when the ATOFMS was deployed ranged from 1 to 65% with an average contribution of 17%, while the remaining mass was attributed to other local and regional sources. These findings demonstrate the impact of metalworking facilities on air quality downwind and provide useful single particle signatures for future source apportionment studies in communities impacted by metalworking emissions.

Characterization of Equivalent Black Carbon at a regional background site in Central Europe: Variability and source apportionment☆.

Characterizing Black Carbon (BC) at regional background areas is important for better understanding its impact on climate forcing and health effects. The variability and sources of Equivalent Black Carbon (EBC) in PM10 (atmospheric particles with aerodynamic diameter smaller than 10 µm) have been investigated during a 5-year measurement period at the National Atmospheric Observatory Kosetice (NAOK), Czech Republic. Ground based measurements were performed from September 2012 to December 2017 with a 7-wavelength aethalometer (AE31, Magee Scientific). The contributions of fossil fuel (EBCff) and biomass burning (EBCbb) were estimated using the aethalometer model. Seasonal, diurnal and weekly variations of EBC were observed that can be related to the sources fluctuations and transport characteristic of pollutants predominantly associated with regional air masses recirculating over the Czech Republic and neighboring countries. The absorption Ångström exponent (α-value) estimated in summer (1.1 ± 0.2) was consistent with reported value for traffic, while the mean highest value (1.5 ± 0.2) was observed in winter due to increased EBCbb accounting for about 50% of the total EBC. This result is in agreement with the strong correlation between EBCbb and biomass burning tracers (levoglucosan and mannosan) in winter. During this season, the concentrations of EBCbb and Delta-C (proxy for biomass burning) reached a maximum in the evening when increasing emissions of wood burning in domestic heating devices (woodstoves/heating system) is expected, especially during the weekend. The diurnal profile of EBCff displays a typical morning peak during the morning traffic rush hour and shows a decreasing concentration during weekends due to lower the traffic emission.

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.

Is vetiver grass of interest for the remediation of Cu and Cd to protect marketing gardens in Burkina Faso?

In Burkina-Faso, urban vegetable agriculture is often characterized by urban solid waste fertilizer inputs containing heavy metals such as Cu and Cd. Thus, the relevance of surrounding urban vegetable plots with vetiver hedges to reduce environmental pollution by Cu and Cd was investigated by adsorption studies and pot experiments. Vetiver biomass, its metal contents and, its total and MgCl2 extractable soil metals were monitored over 6months in the presence of a mixture of metal at two concentrations: 2-10 and 100-500mgkg(-1), for Cd and Cu, respectively. The Freundlich adsorption coefficient (Kf) values increased after vetiver growth and were significantly higher for vertisol than for lixisol. After 6months, the vetiver that was grown on lixisol accumulated more metal, increasing up to 4635mgkg(-1) for Cu and to 21.8mgkg(-1) for Cd, than did the vetiver that was grown on vertisol, increasing up to 1534mgkg(-1) for Cu and to 7.2mgkg(-1) for Cd. The metal bioconcentration factor, which was significantly higher for Cd, increased with the applied concentration and ranged from 1.6 to 14 for Cu and from 2.3 to 22 for Cd. Additionally, the translocation factors were higher for Cd (0.38-7.3) than for Cu (0.07-2.6), and the translocation was easiest from lixisol than from vertisol. Thus our results demonstrate the ability of vetiver for Cu and Cd phytoremediation in Burkina Faso soils. Nevertheless, these results should be confirmed across the field to advocate the establishment of vetiver hedges.