Assessment of ecological risk from bioaccumulation of PCDD/Fs and dioxin-like PCBs in a coastal lagoon

The ecological risk posed by dioxin-like PCBs and PCDD/Fs congeners mixtures in five organisms representative of the food web of the lagoon of Venice (Italy) was estimated by applying the US-EPA [US-EPA. Guidelines for Ecological Risk Assessment. EPA/630/R-95/002F. Final Report. U.S. Environmental Protection Agency, Washington, DC; 1998.] procedure. Experimental concentrations of dioxin-like PCBs and PCDD/Fs in sediments, water, and organisms in six lagoon zones were used to define the spatial distribution of the pollutant homolog patterns. The Principal Component Analysis of homolog patterns in biota permitted to remark the difference between PCDD/Fs and dioxin-like PCBs bioaccumulation. Dioxin-like PCBs were found almost unaltered in all selected organisms, while PCDD/Fs homologs underwent an enrichment of low chlorinated furans in fish. The ecological risk for the dioxin-like PCBs and PCDD/Fs was estimated in the selected lagoon zones according to the Hazard Quotient approach by comparing the biota experimental concentrations in TEQ with an Internal No Effect Concentration of the 2,3,7,8-TCDD, estimated from both Ambient Quality Criteria and literature toxicity data. A high potential risk was found for benthic biota (i.e. clam and crab) and for mussel, while a negligible risk was estimated for fish. Moreover, the ecological risk resulted higher in the central part of the lagoon, and lower in the northern lagoon. Finally, the comparison between the TEQ concentrations of each homolog in biota and the estimated ecological risk highlighted that the risk was determined essentially by lower chlorinated PCDD/Fs (i.e. pentachloro and hexachloro PCDD/Fs), and by pentachloro-PCBs. These compounds should be regarded as homologs of concern and preferentially investigated in environmental monitoring of sediment, water, and biota.     

Environmental quality of transitional waters: the lagoon of Venice case study

The health status of European aquatic environments, including transitional waters such as coastal lagoons, is regulated by the Water Framework Directive (WFD), which requires the classification of the water bodies' environmental quality and the achievement of a good ecological status by 2015. In the Venice lagoon, a transitional water body located in the northeastern part of Italy, the achievement of a good ecological status is hampered by several anthropogenic and natural pressures, such as sediment and water chemical contamination, and sediment erosion. In order to evaluate the lagoon's environmental quality according to the WFD (i.e. 5 quality classes, from High to Bad), an integrated Weight-of-Evidence methodology was developed and applied to classify the quality of the lagoon water bodies, integrating biological, physico-chemical, chemical, ecotoxicological, and hydromorphological data (i.e. Lines of Evidence, LOE). The quality assessment was carried out in two lagoon habitat typologies (previously defined on the basis of morphological, sediment, and hydrodynamic characteristics) which were selected taking into account the ecological gradient from sea to land, and the differences in anthropogenic pressure and contamination levels. The LOE classification was carried out by using indicators scored by comparing site specific conditions to reference conditions measured in lagoon reference sites, or provided by local, national or European regulations (e.g. Environmental Quality Standards, EQS, for chemicals). Finally, the overall quality status for each water body was calculated by a probabilistic approach, i.e. by reporting the final result as the frequency distribution of quality classes. The developed procedure was applied by using data and information concerning selected LOE and collected from monitoring programs and research studies carried out in the last 15 years in the lagoon of Venice. A set of sampling stations characterized by spatially and temporally coherent information for each LOE was selected, and among these stations, potential reference sites for each water body typology were identified. The quality assessment highlighted that there are specific lagoon areas, especially those located near the industrially developed area, which are highly affected by anthropogenic activities, and that chemical contamination is one of the main pressures affecting ecological status (e.g. macro-benthonic biodiversity) in the Venice lagoon. The integrated quality assessment procedure that was developed provided a new tool supporting decision making, as well as lagoon assessment and management.     

Introducing an integrated climate change perspective in POPs modelling, monitoring and regulation

This paper presents a review on the implications of climate change on the monitoring, modelling and regulation of persistent organic pollutants (POPs). Current research gaps are also identified and discussed.Long-term data sets are essential to identify relationships between climate fluctuations and changes in chemical species distribution. Reconstructing the influence of climatic changes on POPs environmental behaviour is very challenging in some local studies, and some insights can be obtained by the few available dated sediment cores or by studying POPs response to inter-annual climate fluctuations. Knowledge gaps and future projections can be studied by developing and applying various modelling tools, identifying compounds susceptibility to climate change, local and global effects, orienting international policies.Long-term monitoring strategies and modelling exercises taking into account climate change should be considered when devising new regulatory plans in chemicals management.     

Reconstruction of historical trends of PCDD/Fs and PCBs in the Venice Lagoon, Italy

Historical trends of PCDD/Fs and PCBs from the year 1900 have been reconstructed for the Venice Lagoon area by using a fugacity-based dynamic multimedia model. A novel approach to estimate the inputs to the system was applied. Emissions to the lagoon were estimated by studying dated sediment cores taken from salt marshes located in the lagoon area. These cores have recently proven to be a suitable tool to reconstruct the temporal trends of atmospheric deposition of POPs. According to the model, concentrations of PCBs and PCDD/Fs in air and water reflect the trends of their production and usage, peaking during the 1960s. The peaks in the sediment were delayed by 5-40 years depending on the congener. Predicted concentrations are in good agreement with experimental results. The most important input parameters, identified by a sensitivity analysis, are the degradation constants, K(ow), the Henry's law constant, vapour pressure, active sediment depth, sediment resuspension, and deposition rates, and water residence time in the lagoon.     

Estimation of PCDD/F distribution and fluxes in the Venice Lagoon,Italy: combining measurement and modelling approaches

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.     

Regional risk assessment for contaminated sites part 1: vulnerability assessment by multicriteria decision analysis

As highlighted in the EU Soil Communication, local contamination is one of the main soil threats and it is often related to present and past industrial activities which left a legacy of a high number of contaminated sites in Europe. These contaminated sites can be harmful to many different receptors according to their sensitivity/susceptibility to contamination, and specific vulnerability evaluations are needed in order to manage this widely spread environmental issue. In this paper a novel comprehensive vulnerability assessment framework to assess regional receptor susceptibility to contaminated site is presented. The developed methodology, which combines multi criteria decision analysis (MCDA) techniques and spatial analysis, can be applied to different receptors recognized as relevant for regional assessment. In order to characterize each receptor, picked parameters significant for the estimation of the vulnerability to contaminated sites have been selected, normalized and aggregated by means of multi criteria decision analysis (MCDA) techniques. The developed MCDA methodology, based on the Choquet integral, allows to include expert judgments for the elicitation of synergic and conflicting effects between involved criteria and is applied to all the geographical objects representing the identified receptors. To test the potential of the vulnerability methodology, it has been applied to a specific case study area in the upper Silesia region of Poland where it proved to be reliable and consistent with the environmental experts' expected results. The vulnerability assessment results indicate that groundwater is the most vulnerable receptor characterized by a wide area with vulnerability scores belonging to the highest vulnerability class. As far as the other receptors are concerned, human health and surface water are characterized by quite homogeneous vulnerability scores falling in the medium-high vulnerability classes, while protected areas resulted to be the less vulnerable receptor with only one protected area falling in the medium vulnerability class. The vulnerability assessment results will support the regional risk assessment for the ranking of potentially contaminated sites at regional scale.     

Organic carbon changes in the surface sediments of the Venice lagoon

The concentrations of total, inorganic and organic carbon in the surface sediment of the central part of the Venice lagoon (31-55 stations) during the month of June in 1987, 1993 and 1998 were recorded. In two stations: San Giuliano and Lido, samples were collected on a monthly basis for 1 year also in different periods. On an average, by considering the whole central lagoon, inorganic carbon (IC) and total carbon (TC) did not show significant changes. In contrast organic carbon (OC) had alternating trends showing a decrease from 1987 to 1993, due to the almost complete disappearance of huge macroalgal biomasses, and a marked increase from 1993 to 1998, because of the high sediment disturbance caused by the catching of the clam Tapes philippinarum Adams & Reeve which had colonised the sediment free of macrophytes. The carbon changes monitored in the two stations studied on a seasonal basis during different years not only confirmed such results, but also enhanced the effects of fishing activities at Lido station and those depending on the disappearance of macroalgae at S. Giuliano. Moreover, this paper underlines the importance of seagrass beds. In fact in the areas colonised by those plants the percentage of fine sediments and organic matter is on the increase, while erosive processes are contrasted.     

Immunotoxicity of carbon black nanoparticles to blue mussel hemocytes

The potential for human and ecological toxicity associated with nanomaterials is a growing area of investigation. In mammalian cells, nanoparticles have been shown to induce inflammation and oxidative stress, and changes in cell signalling and gene expression. As the nanotechnology industries increase production, nanoscale products and by products will enter the aquatic environment, posing a possible threat to aquatic organisms. In particular, filter-feeding organisms may represent a unique target group for nanoparticle toxicology. In this work, the effects of commercial nanosized carbon black (NCB) on the immune cells, the hemocytes, of the bivalve mollusc Mytilus, and the possible mechanisms involved were investigated. The results demonstrate that NCB (1, 5, and 10 microg/ml), did not induce significant lysosomal membrane destabilization, as evaluated by the NR retention time assay. A concentration-dependent uptake of NCB by hemocytes was observed and it was associated by a rapid increase in extracellular lysozyme release, extracellular oxyradical production, and nitric oxide (NO) release. Moreover, at the highest concentration tested, NCB induced significant changes in mitochondrial parameters (decrease mitochondrial mass/number and membrane potential), as evaluated by flow cytometry. The effects of NCB were mediated by rapid activation of the stress-activated MAPKs (Mitogen Activated Protein Kinases) p38 and JNKs, that play a key role in immune and inflammatory responses. The results demonstrate that in mussel hemocytes like in mammalian cells NCB exposure can induce inflammatory processes, and indicate that bivalve immunocytes can represent a suitable model for investigating the effects and modes of action of nanoparticles in the cells of aquatic invertebrates.     

Natural and synthetic endocrine disrupting compounds (EDCs) in water, sediment and biota of a coastal lagoon

We report a survey on the occurrence and distribution of natural (17beta-estradiol, E2; estrone, E1) and synthetic (nonylphenol, NP; nonylphenol monoethoxylate carboxylate, NP1EC; bisphenol-A, BPA; benzophenone, BP; mestranol, MES; 17alpha-ethinylestradiol, EE2; diethylstilbestrol, DES) endocrine disrupting compounds (EDCs) in water, sediment and biota (Mediterranean mussel, Mytilus galloprovincialis) in the Venice lagoon, a highly urbanized coastal water ecosystem that receives both industrial and municipal wastewater effluents. The survey was preceded by the development of tailor made extraction and clean-up procedures for the simultaneous HPLC-ESI-MS determination of all examined EDCs in sediment and biota samples. Satisfactory extraction performances and method detection limits (MDLs) were obtained for almost all EDCs. Most of the selected compounds were found in water and sediment (concentration range: 2.8-211 ng/L, and 3.1-289 microg/kg, d.w., respectively), while only 17alpha-ethinylestradiol and nonylphenol were recorded in biota samples (conc. range: 7.2-240 ng/g, d.w.). 17beta-estradiol and ethinylestradiol contributed mostly to the water estradiol equivalent concentration (EEQ) (1.1-191 ng/L, average: 25 ng/L), while synthetic EDCs (17alpha-ethinylestradiol, diethylstilbestrol) were mainly responsible of the sediment EEQ (1.1-191 microg/kg, average: 71 microg/kg, d.w.). Whenever diethylstilbestrol was not recorded in the sediment, water EEQs were similar to sediment EEQs. A remarkable increase of nonylphenol was observed in sediments over the last decade.