Risk based characterisation of contaminated industrial site using multivariate and geostatistical tools

Human and ecological risk assessment requires the sources, distribution, mobility and environmental behaviour of contaminants to be investigated on a site-specific basis. It often deals with data sets which are relatively small and affected by sampling gaps. In the case of a polycyclic aromatic hydrocarbon (PAH) contaminated industrial site, Kriging interpolation of spatial data and principal component analysis (PCA) proved useful for extracting additional value from the data set. Kriging was adopted for assessing the horizontal and vertical distribution and transport of PAHs in soil. PCA was applied to PAH concentration and relative abundance in soil samples and interpreted on the basis of the PAH physico-chemical and bio-degradation properties. It revealed correlation with the products of a neighbouring factory and the weathering of the lighter PAHs. The geo- and multivariate statistical results were coupled with the previous hydrogeological characterisation of the site to develop a site-conceptual model for use in the exposure scenario modelling for risk assessment.     

Screening ecological risk assessment for the benthic community in the Venice lagoon (Italy)

According to the risk hypothesis: the sediment as source of potential risk for the benthic community, an Ecological Risk Assessment (ERA) based on the quotient method was undertaken. The exposure of the benthic community to different classes of pollutants (metals, chlorinated organic compounds and polynuclear aromatic hydrocarbons) was inferred by estimating the pollutant stocks in the top 15-cm sediment of the whole Venice lagoon, after application of geostatistic techniques. The risk was calculated by comparing the sediment exposure profiles with the ecotoxicological benchmarks for benthic organisms. Kriging based maps of the spatial distribution of the estimated risk for the benthic community over the whole lagoon were obtained. The highest risk, found in the areas nearest to the sources of contamination (e.g., the industrial district of Porto Marghera and the river mouths), was posed by mercury (40% of the sampling stations showed exposure levels higher than the Probable Effect Level), arsenic and nickel (75% of the sampling stations exceeded the Threshold Effect Level).     

Recording the occurrence of trophic level changes in the lagoon of Venice over the '90s

Four areas of the Venice lagoon, placed near the Malamocco mouth (Alberoni, st. A), in the Lido watershed (Sacca Sessola, st. B) and near the mainland under the influence of freshwater and urban (San Giuliano, st. C) or industrial (Fusina, st. D) effluents were monitored in two periods: 1989-92 and 1998-99 in order to quantify some environmental changes (macroalgal and phytoplankton biomass, nutrient concentrations, physico-chemical variables) occurred in both the water column and the surface sediment over the '90s. Stations B and C, two areas particularly affected by macroalgae exhibited a biomass of ca. 20 and 8 kg WW m(-2), respectively, during 1989-90. In 1998-99 maximum densities decreased to ca. 0.3 and 0.01 kg WW m(-2). During that period, phytoplankton also decreased significantly both in peaks (Chl a: from 58-86 to 4.0-3.5 microg dm(-3)) and mean values (Chl a: from 9.1-10.3 to 1.3-1.4 microg dm(-3)), especially at sts. C and D. As far as nutrient concentrations are concerned, a different trend was observed in the water column and in the surface sediment, mainly because of the reduction of the primary producers and the disappearance of anoxic crises. In 1998-99 reactive phosphorus (RP) in the water column was up to ca. 3 times as high as in 1989-92. Conversely, dissolved inorganic nitrogen (DIN) was not significantly changed. In 1998-99 the 5 cm sediment top layer at sts. B, C, displayed a significant total nitrogen (TN) and total phosphorus (TP) decrease (TN annual mean: from 1.29 and 2.79 mg DW g(-1) to 0.69 and 1.47 mg DW g(-1), respectively; TP: from 401 and 626 microg DW g(-1) to 360 and 455 microg DW g(-1)). A different result was found at st. A which in 1998-99 was colonised by the seagrass Zostera marina L. That station showed a TN sediment increase from 0.25 to 0.67 mg DW g(-1) and a TP decrease from 455 to 350 microg DW g(-1). Station D, which did not show any macrophyte biomass coverage either in 1992-93 or in 1998-99, exhibited negligible differences. Besides the monitoring of biomasses and nutrients, significant changes related to oxygen concentration, water transparency, pH and E(h) and sediment rates were also recorded.     

Sedimentation rates and erosion processes in the lagoon of Venice

Since the early 1990s in the lagoon of Venice, especially in the central basin, the surface sediment underwent high re-suspension and sedimentation changes and water turbidity increased both because of the disappearance of the macroalgal coverage and the harvesting of the Manila clam Tapes philippinarum Adams and Reeve, which had rapidly colonised the bottom free of macrophytes. Clams are harvested with hydraulic and mechanical dredges which remove and re-suspend surface sediments causing the transport and loss of the finest materials. Sediment transport and re-deposition in the lagoon have been monitored with sediment traps placed onto the bottoms near the Malamocco mouth (st. A), the Lido watershed (st. B) and the mainland (sts. C and D). From 1989-1993 to 1998-1999 sedimentation rates increased significantly at st. A (from 41 to 228 kg DW m(-2) year(-1)), st. B (from 65 to 760 kg DW m(-2) year(-1)) and st. C (from 140 to 721 kg DW m(-2) year(-1)), while at st. D sedimentation rates increased only by ca. 20%. In parallel sediment grain-size changed with a loss of the finest fraction especially near the mainland. The erosion or sedimentation status, acquired by utilizing sedimentation devices placed onto the bottoms, showed that sts. B, C, D were affected by sediment losses, while st. A, populated by seagrasses and characterised by seasonal variations which depend on the shoot development, did not show any significant bathymetric change on an annual basis. The highest sediment erosion was recorded at st. D (ca. 3.6 cm year(-1)) whereas a loss of ca. 1.5 and 0.5 cm year(-1) was found at sts. C and B, respectively, which accounted for a mean loss in the central lagoon of ca. 1.2 million tonnes year(-1). Those data agree with the previous indirect estimation of sediment loss which was based on the number of fishing boats operating in the lagoon on an annual basis.     

Temporal trends in the sources of PCDD/Fs to and around the Venice Lagoon

Two salt marsh cores were collected from the Venice Lagoon, Italy, and analysed for PCDD/Fs. The samples were undisturbed and had an approximately constant accumulation rate. Radiochemical chronologies were established for the different core sections. The PCDD/F pattern in the surficial layers was very similar to that of atmospheric deposition measured in the same area. However, the pattern changed with increasing depth and was very different in the deeper sections, where the highest PCDD/F concentrations were measured. This layer was dated around the 1950s. Deeper layers have a profile similar to the surficial one. Undisturbed salt marsh cores appear to be a reliable tool for the reconstruction of temporal trends in the atmospheric deposition of persistent organic pollutants. It is proposed that the trends in the core reflect atmospheric deposition that probably results from the sum of two different contributions: emissions of the industrial district of Porto Marghera on the edge of the lagoon and the regional background.     

Characterization of contaminated soil and groundwater surrounding an illegal landfill (S. Giuliano,Venice, Italy) by principal component analysis and kriging

The characterization of a hydrologically complex contaminated site bordering the lagoon of Venice (Italy) was undertaken by investigating soils and groundwaters affected by the chemical contaminants originated by the wastes dumped into an illegal landfill. Statistical tools such as principal components analysis and geostatistical techniques were applied to obtain the spatial distribution of chemical contaminants. Dissolved organic carbon (DOC), SO4(2-) and Cl- were used to trace the migration of the contaminants from the top soil to the underlying groundwaters. The chemical and hydrogeological available information was assembled to obtain the schematic of the conceptual model of the contaminated site capable to support the formulation of major exposure scenarios, which are also provided.     

Aerosolization of an anionic surfactant (LAS) and dissolved organic carbon (DOC) under laboratory conditions.

Aerosolization of natural salt and brackish waters under laboratory conditions is responsible for the transfer of synthetic surfactants such as linear alkylbenzene sulphonate (LAS) from water to the atmosphere. Excluded the lagoon sample which stands apart, on the average ca. 45% of the LAS present at concentrations between 0.1 and 4.1 microg l(-1) in the tested coastal and offshore marine and lagoon waters was transferred to the aerosol extract. The distribution of the individual LAS homologs in the aerosol is very similar to that in water, which indicates no preferential removal from the bulk water of any LAS homolog. The fraction of dissolved organic carbon (DOC) undergoing aerosolization under the same conditions for each tested sample was on an average ca. 3.3%, corresponding to ca. 5.6 mg l(-1). On the average, the enrichment factor of the sea samples, resulting from the changing of the LAS/DOC ratio before and after aerosolization, was ca. 20.     

Impact of agglomeration and different dispersions of titanium dioxide nanoparticles on the human related in vitro cytotoxicity and genotoxicity

The published results on nanoparticles cytotoxicity and genotoxicity such as titanium dioxide nanoparticles (TiO(2) NPs) are inconsistent, and often conflicting and insufficient. Since different parameters may have impact on the toxicity results, there is need to lay stress on detailed characterization of NPs and the use of different testing conditions for assessment of NPs toxicity. In order to investigate whether dispersion procedures influence NP cytotoxicity and genotoxicity, we compared two protocols giving TiO(2) NP dispersions with different stability and agglomeration states. Detailed primary and secondary characteristics of both TiO(2) NP dispersions in culture media were carried out before toxicological testing; TK6 human lymphoblast cells, EUE human embryonic epithelial cells and Cos-1 monkey kidney fibroblasts were used to assess cytotoxicity (by trypan blue exclusion, proliferation activity and plating efficiency assays) and genotoxicity (by the comet assay). DNA strand breaks were detected by the alkaline comet assay. DNA oxidation lesions (especially 8-oxo-7,8-dihydroguanine, 8-oxoG) were measured with a modified comet assay including incubation with specific repair enzyme formamidopyrimidine DNA glycosylase (FPG). The TiO(2) NPs dispersion with large agglomerates (3 min sonication and no serum in stock solution) induced DNA damage in all three cell lines, while the TiO(2) NPs dispersed with agglomerates less than 200 nm (foetal serum in stock solution and sonication 15 min) had no effect on genotoxicity. An increased level of DNA oxidation lesions detected in Cos-1 and TK6 cells indicates that the leading mechanism by which TiO(2) NPs trigger genotoxicity is most likely oxidative stress. Our results show that the dispersion method used can influence the results of toxicity studies. Therefore at least two different dispersion procedures should be incorporated into assessment of cyto- and genotoxic effects of NPs. It is important, when assessing the hazard associated with NPs, to establish standard testing procedures and thorough strategies to consider the diverse conditions relevant to possible exposures.     

Regional risk assessment for contaminated sites part 2: ranking of potentially contaminated sites

Environmental risks are traditionally assessed and presented in non spatial ways although the heterogeneity of the contaminants spatial distributions, the spatial positions and relations between receptors and stressors, as well as the spatial distribution of the variables involved in the risk assessment, strongly influence exposure estimations and hence risks. Taking into account spatial variability is increasingly being recognized as a further and essential step in sound exposure and risk assessment. To address this issue an innovative methodology which integrates spatial analysis and a relative risk approach was developed. The purpose of this methodology is to prioritize sites at regional scale where a preliminary site investigation may be required. The methodology aimed at supporting the inventory of contaminated sites was implemented within the spatial decision support sYstem for Regional rIsk Assessment of DEgraded land, SYRIADE, and was applied to the case-study of the Upper Silesia region (Poland). The developed methodology and tool are both flexible and easy to adapt to different regional contexts, allowing the user to introduce the regional relevant parameters identified on the basis of user expertise and regional data availability. Moreover, the used GIS functionalities, integrated with mathematical approaches, allow to take into consideration, all at once, the multiplicity of sources and impacted receptors within the region of concern, to assess the risks posed by all contaminated sites in the region and, finally, to provide a risk-based ranking of the potentially contaminated sites.