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 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.