The aim of this study was to understand the contribution of Linear Alkylbenzene Sulfonates (LAS) to the decline of Mediterranean coastal forest exposed to marine aerosols. LAS are a group of synthetic anionic surfactants widely used in the composition of household or industrial detergents and agrochemicals. This study was part of a large project (RISICO) aiming the assessment of the environmental impact of the LAS at multiple levels: biodegradation in the coastal waters, sorption – desorption processes in the sediments, toxicity to the aquatic life and toxicity to the coastal forest (by aerosolisation of the sea water). Previous studies pointed out this group of surfactants as the main cause of the coastal forest decline. However, the quantification of this surfactant in the environmental samples (mainly sea water and foliar deposition) was done using non-specific analytical methods as methylene blue active substances (MBAS), leading to overestimation of the environmental concentrations of LAS. The work hypothesis was that at actual environmental concentrations, the LAS does not play a key role in the foliar uptake of the sea salt deposited on the coastal vegetation by the marine aerosols, therefore the LAS may not be the main cause of the coastal forest decline. The research involved both greenhouse experiments and field measurements. The experimental work was conducted on young Mediterranean trees (Laurus nobilis L., Quercus ilex L. and Pinus halepensis P. Mill.) and investigated the synergistic toxic effects of exposure to simulated marine aerosol contaminated with surfactants. An array of endpoints was used including photosynthetic activity, relative water content, foliar deposition and uptake of salt and LAS, and pigments analysis. The results of those experiments revealed that LAS itself did not have phytotoxic effects. Nevertheless, the surfactant was shown to enhance the foliar uptake of the salt in the tested species, especially in Pinus halepensis, confirming the conclusions of previous studies regarding the sensitivity of this species to polluted marine aerosols. The field work was conducted in San Rossore National Park (Italy) and Porquerolles Island (France) and was focused on evaluating the health status of the Mediterranean forest (Quercus ilex L., Pinus halepensis Mill. and Pinus pinaster Aiton.) and also on quantification of LAS in coastal aerosols using highly specific analytical methods, like the mass spectrometry (MS). The frequencies and extent of injuries in the coastal trees were found to be correlated to the salt but not with the LAS content of the leaves. The concentrations of LAS in the Pinus and Quercus leaves were comparable in the two studied sites but the concentrations of salt were extremely high in San Rossore, suggesting that other factors may determine the excessive salt foliar uptake. The parallel MS and MBAS carried out in the same set of aerosol samples revealed that MBAS measurements were not relevant for LAS concentrations in the marine aerosols. Projecting the experimental results to the real LAS and salt exposure of the coastal forest, we concluded that LAS may play a marginal role in coastal vegetation decline.

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The aim of this study was to understand the contribution of Linear Alkylbenzene Sulfonates (LAS) to the decline of Mediterranean coastal forest exposed to marine aerosols. LAS are a group of synthetic anionic surfactants widely used in the composition of household or industrial detergents and agrochemicals. This study was part of a large project (RISICO) aiming the assessment of the environmental impact of the LAS at multiple levels: biodegradation in the coastal waters, sorption – desorption processes in the sediments, toxicity to the aquatic life and toxicity to the coastal forest (by aerosolisation of the sea water). <p>Previous studies pointed out this group of surfactants as the main cause of the coastal forest decline. However, the quantification of this surfactant in the environmental samples (mainly sea water and foliar deposition) was done using non-specific analytical methods as methylene blue active substances (MBAS), leading to overestimation of the environmental concentrations of LAS. <p>The work hypothesis was that at actual environmental concentrations, the LAS does not play a key role in the foliar uptake of the sea salt deposited on the coastal vegetation by the marine aerosols, therefore the LAS may not be the main cause of the coastal forest decline. <p>The research involved both greenhouse experiments and field measurements. The experimental work was conducted on young Mediterranean trees (Laurus nobilis L. Quercus ilex L. and Pinus halepensis P. Mill.) and investigated the synergistic toxic effects of exposure to simulated marine aerosol contaminated with surfactants. An array of endpoints was used including photosynthetic activity, relative water content, foliar deposition and uptake of salt and LAS, and pigments analysis. The results of those experiments revealed that LAS itself did not have phytotoxic effects. Nevertheless, the surfactant was shown to enhance the foliar uptake of the salt in the tested species, especially in Pinus halepensis, confirming the conclusions of previous studies regarding the sensitivity of this species to polluted marine aerosols. <p>The field work was conducted in San Rossore National Park (Italy) and Porquerolles Island (France) and was focused on evaluating the health status of the Mediterranean forest (Quercus ilex L. Pinus halepensis Mill. and Pinus pinaster Aiton.) and also on quantification of LAS in coastal aerosols using highly specific analytical methods, like the mass spectrometry (MS). The frequencies and extent of injuries in the coastal trees were found to be correlated to the salt but not with the LAS content of the leaves. The concentrations of LAS in the Pinus and Quercus leaves were comparable in the two studied sites but the concentrations of salt were extremely high in San Rossore, suggesting that other factors may determine the excessive salt foliar uptake. The parallel MS and MBAS carried out in the same set of aerosol samples revealed that MBAS measurements were not relevant for LAS concentrations in the marine aerosols. Projecting the experimental results to the real LAS and salt exposure of the coastal forest, we concluded that LAS may play a marginal role in coastal vegetation decline. <p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Marine aerosols have attracted increasing attention over the past 15 years because of their potential significance for global climate modelling. The size distribution of these aerosols extends from super-micrometer sea salt mode particles down through 150 nm accumulation mode particles, 40 nm Aitken mode particles and nucleation mode particles which extend from 25 nm right down to clusters of a few molecules. The process by which the submicrometer modes form and grow and their composition have remained topics of debate throughout this time in large part because of the difficulties associated with determining their composition and relating it to proposed models of the formation process. The work compared the modality of marine aerosol influencing the South-east-Queensland region with that of other environmental aerosols in the region. The aerosol was found to be consistent with marine aerosols observed elsewhere with concentrations below 1000 cm-3 and frequently exhibiting the distinct bimodal structure associated with cloud processing, consisting of an Aitken mode at approximately 40 nm, an accumulation mode in the range 100-200 nm and a coarse mode attributed to sea salt between 600 and 1200 nm. This work included the development of two new techniques for aerosol research. The first technique measures aerosol density using a combination of aerosol size distribution and gravimetric mass concentration measurements. This technique was used to measure the density of a number of submicrometer aerosols including laboratory generated NaCl aerosol and ambient aerosol. The densities for the laboratory generated aerosols were found to be similar to those for the bulk materials used to produce them. The technique, extended to super-micrometer particle size range may find application in ambient aerosol research where it could be used to discriminate between periods when the aerosol is dominated by NaCl and periods when the density is more representative of crustal material or sulfates. The technique may also prove useful in laboratory or industrial settings for investigating particle density or in case where the composition is known, morphology and porosity. The second technique developed, integrates the existing physicochemical techniques of volatilisation and hygroscopic growth analysis to investigate particle composition in terms of both the volatilisation temperatures of the chemical constituents and their contribution to particle hygroscopic behaviour. The resulting volatilisation and humidification tandem differential mobility analyser or VH-TDMA, has proven to be a valuable research tool which is being used in ongoing research. Findings of investigations relating the composition of the submicrometer marine aerosol modes to candidate models for their formation are presented. Sea salt was not found in the numerically dominant particle type in coastal nucleation mode or marine Aitken and accumulation modes examined on the Southeast Queensland coast during periods where back trajectories indicated marine origin. The work suggests that all three submicrometer modes contain the same four volatile chemical species and an insoluble non-volatile residue. The volatility and hygroscopic behaviours of the particles are consistent with a composition consisting of a core composed of sulfuric acid, ammonium sulfate and an iodine oxide coated with a volatile organic compound. The volume fraction of the sulfuric acid like species in the particles shows a strong dependence on particle size.