Spatio-temporal variability of airborne bacterial communities and their correlation with particulate matter chemical composition across two urban areas.

The study of spatio-temporal variability of airborne bacterial communities has recently gained importance due to the evidence that airborne bacteria are involved in atmospheric processes and can affect human health. In this work, we described the structure of airborne microbial communities in two urban areas (Milan and Venice, Northern Italy) through the sequencing, by the Illumina platform, of libraries containing the V5-V6 hypervariable regions of the 16S rRNA gene and estimated the abundance of airborne bacteria with quantitative PCR (qPCR). Airborne microbial communities were dominated by few taxa, particularly Burkholderiales and Actinomycetales, more abundant in colder seasons, and Chloroplasts, more abundant in warmer seasons. By partitioning the variation in bacterial community structure, we could assess that environmental and meteorological conditions, including variability between cities and seasons, were the major determinants of the observed variation in bacterial community structure, while chemical composition of atmospheric particulate matter (PM) had a minor contribution. Particularly, Ba, SO4 (2-) and Mg(2+) concentrations were significantly correlated with microbial community structure, but it was not possible to assess whether they simply co-varied with seasonal shifts of bacterial inputs to the atmosphere, or their variation favoured specific taxa. Both local sources of bacteria and atmospheric dispersal were involved in the assembling of airborne microbial communities, as suggested, to the one side by the large abundance of bacteria typical of lagoon environments (Rhodobacterales) observed in spring air samples from Venice and to the other by the significant effect of wind speed in shaping airborne bacterial communities at all sites.

Multivariate analysis as a tool for Ion Beam Induced Luminescence (IBIL) spectra interpretation.

Multivariate analysis is used to identify the number and wavelength position of components evolving during irradiation with different rates in Ion Beam Induced Luminescence (IBIL) spectra. The method, based on the study of the eigenvectors of the matrix whose elements are the luminescence intensity values for different wavelengths and fluences, is tested on two different simulated cases and on experimental IBIL spectra collected from a polysiloxane scintillators.

Atmospheric bulk deposition to the lagoon of Venice Part I. Fluxes of metals, nutrients and organic contaminants.

First available data on atmospheric fall-out were provided by sampling monthly bulk depositions in four sites inside the Lagoon of Venice (550 km2). Sampling was carried out monthly during the period July 1998-July 1999, in one site near an industrial area (Porto Marghera; site D), another site in the city of Venice (site A), and the remaining two in the southern- and northernmost ends of the Lagoon (Valle Figheri, site C; Valle Dogà site B). The following determinations were carried out for each samples: pH, conductivity, grain-size, particulate load, and dissolved nutrients (N, P). Samples were then subdivided into soluble and insoluble fractions, and Al, Ca, Na, K, Mg, Si, Mn, Fe, Zn, Ni, Cr, Cu, Pb, Cd, As, Hg, Ti, V, S, P, Se and Sb were analysed on both fractions. Total organic micropollutants (PAH, PCB, HCB, DDT, PCDD/F) were measured. As regards particle size distribution, there was great variability among sampling sites. The percentage of the < or =2 microm grain-size fraction was higher in the southern and northern ends of the Lagoon. Small differences were found among sites for major elements, whereas higher variability was observed for inorganic and organic micropollutants, with standard deviations between 20% and 60% of the fluxes measured. Major differences in annual fluxes between the most polluted sites (mostly D and A) and background (site B) were seen for Cd (0.26 vs. 0.06 mg m(-2) year(-1)), Hg (41 vs. 15 microg m(-2) year(-1)), PCB ( approximately 2500 vs. approximately 500 ng m(-2) year(-1)) and HCB ( approximately 8000 vs. approximately 1000 ng m(-2) year(-1)). Comparisons with previous data, collected in the periods 1993-1994 and 1995-1997, were only available for a few trace metals. A definite decline in the annual Pb flux in the city of Venice was detected, from 18 to 13 mg m(-2) in 1996/1997 and 1995/1996 respectively, to approximately 5 mg m(-2) in the present study. Total annual deposition was calculated by means of two different methods, which gave very similar results: (i) the mean value of deposition in the four sites was multiplied by lagoon area (550 km2); (ii) the monthly rain isopleths were combined to normalize deposition values. The figures are: 15-34 kg of Hg and Sb, approximately 200 kg of As, approximately 100 kg of Cd and PAH, 0.7-1.3 tons of Cr, Ni and V, more than 2 tons of Cu and Pb, 17 of Zn, 55 of total P, approximately 200 of Al, and 3900 of DIN. Total fluxes of organics inside the lagoon were: PAH approximately 100 kg; HCB approximately 1 kg; DDT approximately 0.4 kg. PCB and PCDD/F fluxes were approximately 500 g and approximately 10 g, corresponding respectively to 0.1 and 0.4 g I-TE. The correlations between fluxes of inorganic micropollutants and grain-size were significant. Multivariate statistical analysis was applied to investigate more accurately relationships between the insoluble and dissolved fractions of inorganic micropollutants and grain-size fractions. In particular, significant correlations were highlighted between the dissolved fraction of As and the < or =1 mum particle size fraction. Relations between levels of SigmaPCDDF, SigmaPCDD, PCB and PAH congeners and grain-size revealed significant correlation coefficients for the remote sites (B, C), and none in the urban and industrial sites (A, D). In particular, significant correlations were highlighted between SigmaPCDDF, SigmaPCDD and particle size fraction < or =2 mum, and between benzo(a)pyrene and PCB 167 and particle size fraction 4-8 mum.

Atmospheric bulk deposition to the Lagoon of Venice Part II. Source apportionment analysis near the industrial zone of Porto Marghera, Italy.

Multivariate statistical analyses were applied to measurements of atmospheric deposition of total particulate (TSP), inorganic elements (Al, Ca, Na, K, Mg, Si, Mn, Fe, Zn, Ni, Cr, Cu, Pb, Cd, As, Hg, V and S) and organic compounds (PAH, PCB, HCB and PCDD/F) collected in four stations, all located in the Lagoon of Venice. Aerosols at the scale of the basin (i.e., within a distance of 20 km) were mainly characterised by two end-members, one natural (composed of mineral particulate and marine spray) and one anthropogenic (with at least two different source components), affecting the sites in various ways. Variability at the two distant (>20 km) sites (Valle Dogà, Valle Figheri) was mainly due to natural components, whereas the other two stations (city of Venice, Dogaletto, approximately 5 km) were mainly impacted by industrial (and urban) sources. Total annual inputs were compared with the limits recently set by law (maximum allowed discharge=MAD). In the year of study, MAD values were exceeded for total As, Cd, Hg, Pb, dissolved Zn, PAH and PCDD/F. These results indicate that industrial sources gave rise to a quasi-permanent compositional (background) effect near the industrial area. The risk associated with atmospheric deposition should be quantified within the DSPIR framework to avoid future negative consequences in populations living in the vicinity of Porto Marghera.

Measurement of atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in the Lagoon of Venice, Italy.

Data on atmospheric fall-out of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were provided by collecting bulk deposition in four stations inside the Lagoon of Venice. A total of 44 monthly samples was collected during the period July 1998-July 1999 in one site near an industrial area (Porto Marghera), one site in the city of Venice, and two sites in the southern- and northernmost ends of the Lagoon. Fluxes of PCDD/Fs were between 0.1 and 470 pg m(-2) d(-1), corresponding to 0-9.2 pg of 2,3,7,8-TCDD equivalents (TEQ) m(-2) d(-1), with a gradient increasing from remote to urban/industrial stations. Thus, annual deposition of PCDD/Fs to the Lagoon (total area=550 km2), calculated with various methods, turned out to be approximately 12 g, corresponding to approximately 400 mg TEQ. Significant differences were found among the stations, with a clear fingerprinting signature (PCDF/PCDD>1) of the deposition collected near Porto Marghera, and a reversed pattern (PCDF/PCDD<1) in the rest of the Lagoon, which pattern was similar to the sediments collected in the same locations. Lastly, the amount of bulk sigmaTEQ of all stations was compared with the guide values for dioxins in depositions proposed by De Fré et al. [Organohalogen Compounds 45 (2000) 324].

Atmospheric input of organic pollutants to the Venice Lagoon.

The atmospheric deposition of dioxins and furans (PCDD-Fs), dioxin-like polychlorobyphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and hexachlorobenzene (HCB) was determined in the Lagoon of Venice. Sampling was carried out monthly, for a total of 13 months (July 1998-July 1999) using "bulk" samplers (passive collectors of wet and dry depositions) at four sites, inside the lagoon and close to its edge. Calculated PCDD-F loadings to the Lagoon turned out to be quite homogeneous, their range being approximately 10-20 ng m-2 y-1, whereas in the station located close to the industrial zone of Porto Marghera the value was approximately 50 ng m-2 y-1. PCB deposition in the industrial fallout sampling site and in the city centre of Venice was approximately 2500 ng m-2 y-1, that is, almost five times higher than the values measured at the northern and southern lagoon stations. HCB annual loading (approximately 8000 ng m-2 y-1) was almost six times higher in the industrial zone than in the other sites (approximately 1500 ng m-2 y-1). PAH loadings in the city centre of Venice and at Porto Marghera were 314 and 389 micrograms m-2 y-1, respectively. The amount of 2,3,7,8-TCDD equivalents (TEQ) of PCDD-Fs and PCBs in the Venice and Porto Marghera bulk depositions was compared with the guideline value of 15 pg m-2 d-1 for dioxins in depositions proposed by De Fré et al. (1998). Moreover, as some of the effects which drive the risk assessment of dioxin-like compounds were also observed after exposure to other molecules, the TEQs of PAHs and HCB were also calculated: nine out of 13 samples exceeded the guideline value. Lastly, an atmospheric emission source related to vinyl chloride monomer production, which may affect atmospheric deposition on the whole Lagoon, is reported in the industrial zone of Porto Marghera.