Innovative experimental approach for spatial mapping of source-specific risk contributions of potentially toxic trace elements in PM10.

Exposure to potentially toxic trace elements (PTTEs) in inhalable particulate matter (PM10) is associated with an increased risk of developing cardiorespiratory diseases. Therefore, in multi-source polluted urban contexts, a spatially-resolved evaluation of health risks associated with exposure to PTTEs in PM is essential to identify critical risk areas. In this study, a very-low volume device for high spatial resolution sampling and analysis of PM10 was employed in Terni (Central Italy) in a wide and dense network (23 sampling sites, about 1 km between each other) during a 15-month monitoring campaign. The soluble and insoluble fraction of 33 elements in PM10 was analysed through a chemical fractionation procedure that increased the selectivity of the elements as source tracers. Total carcinogenic risk (CR) and non-carcinogenic risk (NCR) for adults and children due to concentrations of PTTEs in PM10 were calculated and quantitative source-specific risk apportionment was carried out by applying Positive Matrix Factorization (PMF) to the spatially-resolved concentrations of the chemically fractionated elements. PMF analysis identified 5 factors: steel plant, biomass burning, brake dust, soil dust and road dust. Steel plant showed the greatest risk contribution. Total CR and NCR, and source-specific risk contributions at the 23 sites were interpolated using the ordinary kriging (OK) method and mapped to geo-reference the health risks of the identified sources in the whole study area. This also allowed risk estimation in areas not directly measured and the assessment of the risk contribution of individual sources at each point of the study area. This innovative experimental approach is an effective tool to localize the health risks of spatially disaggregated sources of PTTEs and it may allow for better planning of control strategies and mitigation measures to reduce airborne pollutant concentrations in urban settings polluted by multiple sources.

The roles of carbohydrates, proteins and lipids in the process of aggregation of natural marine organic matter investigated by means of 2D correlation spectroscopy applied to infrared spectra.

In this paper the marine organic matter soluble in an alkaline medium called extractable humic substance (EHS), was extracted from three sediment samples of Tyrrhenian Sea and separated by precipitation at pH 2 in the two fractions of fulvic acids (FAs) and humic acids (HAs). FAs were further fractionated in seven sub-samples of different molecular weight (mw) by means of seven different ultrafiltration membranes operating in the range between mw<1 kDa and mw>100 kDa. Then the qualitative composition of each sample of fractionated FAs and HAs was studied by means of one-dimensional Fourier transform infrared spectroscopy in reflectance mode (FTIR-DRIFT) and by two-dimensional (2D) correlation spectroscopy both in wavelength-wavelength (WW) and in sample-sample (SS) mode. The application of 2D correlation WW spectroscopy allows to elucidate the different roles played by carbohydrates and proteins with respect to some lipid compounds such as fatty acids and ester fatty acids during the process of aggregate formations from mw approximately 1 kDa to higher size aggregates. In addition, 2D correlation WW spectroscopy allows to observe some peculiar interactions between carbohydrates and proteins in the formation of EHS aggregates, interactions which vary from a sample to another sample. The results of 2D correlation SS spectroscopy confirm the general evidences obtained by 2D WW spectroscopy and moreover, they also describe the formation of EHS aggregates as a complex process where evolutionary links and connectivity between aggregates of neighbour molecular size ranges are not evident. Two-dimensional correlation spectroscopy applied to FTIR spectroscopy shows to be a powerful tool for the investigation of the mechanisms involved in EHS aggregation because it supports the acquisition of structural information which sometimes can be hardly obtained by one-dimensional FTIR spectroscopy.