Karine Deboudt

European isotopic signatures for lead in atmospheric aerosols: a source apportionment based upon 206Pb/207Pb ratios

To investigate the capability of the lead isotope signature technique to support a source apportionment study at a Continental scale, atmospheric particulate matter was collected at Cap Gris-Nez (Eastern Channel, northern France), over one year (1995-1996). Four days retrospective trajectories of air masses were available during each sampling experiment. Twenty-eight samples, for which the origin of aerosols was unambiguously determined, were selected for isotopic measurements. Considering the Enrichment Factors, EF(Crust) of lead and its size distribution, we show that lead is mostly from anthropogenic origin and mainly associated with [0.4 < diameter < 0.9 microm] particles. The extent to which various Continental sources influence the lead abundance in aerosols is exhibited by considering both the lead concentration and the origin of air masses. Lead concentration is higher by a factor of approximately seven, when air masses are derived from Continental Europe, by comparison with marine air masses. Taking into account these concentrations and the vertical movements of air masses, we compare the different isotopic compositions using a statistical non-parametric test (Kolmogorov-Smirnov). We produce evidence that, for most of the cases, air masses originating from Continental Europe exhibit a more radiogenic composition (1.134 < 206Pb/207Pb < 1.172) than air masses coming from the United Kingdom (1.106 < 206Pb/207Pb < 1.124). Generally, lead isotopic compositions in aerosols are clearly distinct from the gasoline signatures in European countries, strongly suggesting that automotive lead is no longer the major component of this metal in the air. Gasoline and industrial isotopic signatures could explain the origin of lead in our aerosol samples. A source apportionment based upon 206Pb/207Pb ratios, suggests that the difference between British (206Pb/207Pb = 1.122 +/- 0.038) and Continental (206Pb/207Pb = 1.155 +/- 0.022) signatures may be largely explained by differences in the petrol lead content of aerosols (23-62% in Great Britain vs. 10-36% in Continental Europe).

Cd, Cu, Pb AND Zn CONCENTRATIONS IN ATMOSPHERIC WET DEPOSITION AT A COASTAL STATION IN WESTERN EUROPE

Bulk rainfalls were sampled during ten months in the Eastern Channel (Northern France). Chloride and sodium are the heavily loaded major ions in wet deposition, indicating a high influence of seasalt. However, the presence of heavy metals is independent of seasalt emissions and various anthropogenic sources should have an impact on their atmospheric concentrations.The comparison between heavy metals concentrations, always ranked as [Zn] ≫ [Pb] > [Cu] ≫ [Cd], with other values obtained during the same period on European coastal or on urban sites, confirms that ourwestern European station is in a semi-rural area where no local source strongly influences the abundance of atmospheric heavy metals. This semi-rural site could be disturbed by medium and/or long range transportepisodes.The observation of literature data confirms a decrease of Cd, Cu and Pb concentrations in rain waters from the beginning of the nineties. On the other hand, no sharp evolution has been observed for zinc concentrations.The structuring of data by clustering has permitted to extract five clusters, including four different types of origins. Two marine clusters, with relatively low levels of heavy metals, are opposite to three other clusters with higher heavy metal levels and a more important impact of continental polluted sources. In 47% of cases, the heavy metals collected at Cap Gris-Nez could originate from British Islands or north western Europe.Heavy metals fluxes show that this rural coastal European site has a level of contamination higher than those measured in remote area. The wet depositions of heavy metals to the English channel and the southern bight of the north sea are not negligible in the evaluation of global fluxes for this area, representing from 20 to 70% of the total input (riverine, direct and atmospheric inputs).

Assessment of pollution aerosols sources above the Straits of Dover using lead isotope geochemistry.

We assess the capability of lead isotopes to study the transport of pollution aerosols above the Straits of Dover by collecting atmospheric aerosols above the Eastern Channel and the Southern Bight of the North Sea. During the same period, we characterized the lead isotopic signature of the main industrial sources on the French coast near the Straits of Dover. Urban and automobile-derived aerosols were also collected. Due to the phasing out of lead in gasoline, the urban isotopic composition (206Pb/207Pb = 1.158 +/- 0.003) has become more radiogenic, although it is highly variable. On a regional scale, major industrial emissions have a well-defined isotopic composition (1.13 < 206Pb/207Pb < 1.22), more radiogenic than the petrol-lead signature (1.06 < 206Pb/207Pb < 1.12). These results together with those measured near the main coastal highway show that the automobile source has become a minor component of particulate lead in air. On a local scale, Dunkerque, the most urbanized and industrialized area along the Straits of Dover, may transiently control elevated lead concentrations. Except for the occurrence of local and regional range transport episodes, lead concentrations in the Straits of Dover can be related to remote or semi-remote pollution source emissions. Combining air mass retrospective trajectories and related lead abundances and isotopic compositions, it can be shown that lead aerosols originating from eastern Europe have an isotopic signature (1.145 < 206Pb/207Pb < 1.169) different from the isotopic composition of west-European lead aerosols (1.111 < 206Pb/207Pb < 1.142). The influence of remote North American sources is suggested, with caution, due to uncertainties in meteorological calculations.

Iron isotopic fractionation in industrial emissions and urban aerosols

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM-EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO(3)) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08 per thousand<delta(56)Fe<+0.80 per thousand) of enriched ores processed by the manufacturer (-0.16 per thousand<delta(56)Fe<+1.19 per thousand). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3-4mum aggregates. In the close urban area, 5km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (delta(56)Fe=0.14+/-0.11 per thousand) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.

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.

Changes in the lead content of atmospheric aerosols above the Eastern Channel between 1982/83 and 1994

Abstract Lead concentrations in atmospheric particulate matter, along the southern coast of the Strait of Dover have been measured during two sampling campaigns, over a 10 year period. The results point out that lead concentrations have been decreased by a factor of two, from 1982/83 to 1994. This evolution is in good agreement with a general trend to the diminution of lead in atmospheric aerosols above the Eastern Channel and the Southern Bight of the North Sea. It appears that, from 1972 to 1994, lead concentrations have decreased by an order of magnitude, despite the uncertainty of the oldest-values. As established in a similar coastal environment, this decrease in the lead concentrations can be explained by the reduction in the emissions of automotive lead. The evolution of the mass-size distribution is consistent with this last factor; assuming that automotive lead is essentially present in particles smaller than 0.33 μm, the observed decrease of this granulometric class between 1983 and 1994 (7 ng/m 3 ) is close to the measured decrease in the lead concentrations (9 ng/m 3 ). A slight decrease (14%) of the related dry deposition flux has been calculated for the same period. But, if part of the fall-out due to particles larger than 1 μm is approximately constant over the same period (about 430 g/km 2 per year), the submicronic flux exhibits a decrease of 70%.

Fine and Ultrafine Particles in the Vicinity of Industrial Activities: A Review

This review synthesizes the existing knowledge on the characteristics of PM2.5 at sites under the direct influence of industrial emissions, with a specific focus on their morphology, size distributions and chemical composition. Results from online and off-line analytical techniques indicate a high temporal and spatial variability of mass size distribution and chemical composition depending on the type of industrial processes, the sampling distances and frequencies, and the meteorological conditions. Tracers of specific activities have been identified in a number of studies and may help to provide estimates of the relative contribution of pollutant sources from heavily industrialized areas.

Fe and Mn Oxidation States by TEM-EELS in Fine-Particle Emissions from a Fe–Mn Alloy Making Plant

Fine particles were sampled both inside the chimneys and in the near-field of an Fe-Mn-alloy manufacturing plant. The transfer from one point to another point in the environment, as well as the bioavailability and toxicity of these two metals, depend above all on their speciation. The oxidation states of iron and manganese in the collected particles were determined by using transmission electron microscopy coupled with electron energy-loss spectroscopy (TEM-EELS). The mineralogical identity of these metal-rich particles was determined by selected area electron diffraction (SAED) coupled with energy-dispersive X-ray spectroscopy (EDX). This study shows that both iron and manganese in metallic particles are prone to oxidation reactions via gas/particle conversion mechanisms, which take place in the flue gases within the smoke stacks. This phenomenon is more pronounced for the smallest Fe-rich particles. However, no further change of oxidation state of the two elements was observed in the near-field of the plant, after emission into the atmosphere (within <2000 m of the smoke stacks). The oxidation states of iron and manganese remain mainly between +II and +III, which is probably due to short residence time of these particles in the pollution plume.

Scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and aerosol time-of-flight mass spectrometry (ATOFMS) single particle analysis of metallurgy plant emissions

The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe-Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.

The lead content of atmospheric aerosols above the eastern channel : seasonal variability and solubility in a coastal seawater

In order to describe the seasonal variability of the atmospheric lead concentrations above the Eastern Channel, aerosols samples have been collected by bulk filtration at the Cape Gris-Nez (Dover Strait) during one year. A statistical analysis of the obtained time-series from lead concentrations and rain amounts illustrates the geochemical implications of a scavenging process: when precipitations become lower than the average rain events, the lead concentrations become higher than the mean values and reciprocally. On a global scale, the lead concentrations over the Eastern Channel and the Southern Bight of the North Sea have decreased by about one order of magnitude since fifteen years. Lead concentrations have been compared to the origin of the collected air masses. The use of the back-trajectories permits us to classify the origins of the air masses among five geographical sectors relevant to the position of our sampling site: Atlantic Ocean and English Channel; North Sea; British Islands; Southern and Western Europe; Scandinavia and Central Europe. Continental sectors show greater lead concentrations than marine and semi-continental sectors, by a factor of about 3 to 7. These results are in a good agreement with the assumption according to which the atmospheric lead is mainly associated with emissions from heavy industrialised and urbanised areas, especially from automotive origin. Under our experimental conditions, the solubility in a coastal seawater for ‘continental’ lead is different from the one of ‘maritime’ lead. These dissolution experiments are developed in order to ultimately answer to the questions ‘how does the dry fall-out scatter into the upper layer of the seawater mass, regarding as a chemical system?’ and more particularly ‘what is the part of the heavy metals transported via the atmosphere which is rapidly transferred into the dissolved phase, i. e. under a labile form potentially available for the interfacial organisms?’