Elsevier

Chemosphere

Volume 54, Issue 9, March 2004, Pages 1309-1317
Chemosphere

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

https://doi.org/10.1016/S0045-6535(03)00249-2Get rights and content

Abstract

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 ∼12 g, corresponding to ∼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 ∑TEQ of all stations was compared with the guide values for dioxins in depositions proposed by De Fré et al. [Organohalogen Compounds 45 (2000) 324].

Introduction

Persistent organic pollutants (POPs) are organic chemicals which are stable to photochemical, chemical and biological decomposition. Most of them would not exist in nature without human activity. POPs are present in the atmosphere in gaseous and aerosol phases. They degrade in the atmosphere as a result of various physical–chemical processes and are removed by wet and dry deposition (UNEP/MAP/WMO, 2001).

Among these substances, dioxins and furans (PCDD/Fs) are not especially produced, but are formed as interim species (by-products) in the process of certain human activities, i.e. industrial processes, fossil fuel combustion, or waste destruction. Air is the main distribution pathway for PCDD/Fs, and PCDD/F composition is therefore influenced by different emissions and congener/homologue-selective transport and atmospheric loss processes (Lohmann and Jones, 1998).

Much work has been done in the past 20 years, to study the presence of PCDD/Fs and other organic chlorine in bottom sediments and aquatic biota in the Lagoon of Venice, Italy. Sources of the contamination are often discharges from the industrial district of Porto Marghera, untreated domestic sewage from the historical city of Venice, and traffic from motorboats and the nearby city of Mestre (Fattore et al., 1997; Di Domenico et al., 1997; Marcomini et al., 1997; Wenning et al., 2000).

Preliminary available data on atmospheric dioxin fall-out were provided by bulk deposition sampling (Rossini et al., 2001), and a budget of dioxin showed that atmospheric deposition accounted for one-quarter of the total load in the Lagoon of Venice (Marcomini et al., 1999a). Data on soils collected around the industrial zone suggested an airborne PCDD/F fall-out effect up to several km downwind (Della Sala et al., 1999).

This paper presents data of 2,3,7,8-substituted PCDD/Fs in atmospheric fall-out, provided by sampling monthly bulk depositions in four stations inside the Lagoon of Venice (550 km2). The purposes of this study were to detect the influence of the industrial district on PCDD/F deposition, to estimate total fluxes inside the lagoon, and to apply statistical multivariate analyses and modelling in order to detect the principal sources of dioxin and furan.

Section snippets

Sampling

Atmospheric depositions were collected by 4 bulk samplers similar to those tested by Horstmann and McLachlan (1997) in a rural environment (Fig. 1). Bulk samplers were polymer structures formed of a cylindrical container and a protection ring to avoid damage by birds and animals. The structure was clamped to a 60 mm pole. A Pyrex bottle with a funnel properly silanised (treated with dimethyldichlorosilane 5% in toluene) was placed in the support. Bulk sampling has been extensively used, since

Meteorology

During the study period the main wind direction observed was NE-N, with mean wind speed of 2–4 m s−1, in agreement with the general anemometry of the area (Carrera et al., 1995). In particular, the main wind direction in site A has been from NE, and the observed frequency for winds from W was always <10% for each deposition sample. Moreover, also the percentage of winds from N at site C has been always <10%. This confirms that these sampling stations have never been downwind from the industrial

Conclusions

  • Bulk deposition provided one-year of data on PCDD/F fluxes, which were independent of rainfall and particle grain-size.

  • Dioxin and furan fluxes from the atmosphere in the Lagoon of Venice were generally lower than those found in Kyoto Bay and similar to those in Hesse, Germany.

  • PCA was used to compare differing PCDD/F patterns among stations, which may indicate different sources.

  • The station D nearest the industrial zone showed signs of contamination from EDC and VCM production.

  • Between 9% and 27%

Acknowledgments

This work was carried out on behalf of the Water Management Authority of Venice, within the framework of actions for safeguarding the Lagoon of Venice (art. 3, L.798/1984––project Orizzonte 2023). Ms Gabriel Walton revised the English text. This is IGM-CNR scientific contribution no. 1279.

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