Winter to spring variations of chromophoric dissolved organic matter in a temperate estuary (Po River, northern Adriatic Sea).

The light absorbing fraction of dissolved organic carbon (DOC), known as chromophoric dissolved organic matter (CDOM) showed wide seasonal variations in the temperate estuarine zone in front of the Po River mouth. DOC concentrations increased from winter through spring mainly as a seasonal response to increasing phytoplankton production and thermohaline stratification. The monthly dependence of the CDOM light absorption by salinity and chlorophyll a concentrations was explored. In 2003, neither DOC nor CDOM were linearly correlated with salinity, due to an exceptionally low Po river inflow. Though the CDOM absorbance coefficients showed a higher content of chromophoric dissolved organic matter in 2004 with respect to 2003, the spectroscopic features confirmed that the qualitative nature of CDOM was quite similar in both years. CDOM and DOC underwent a conservative mixing, only after relevant Po river freshets, and a change in optical features with an increase of the specific absorption coefficient was observed, suggesting a prevailing terrestrial origin of dissolved organic matter.

Time trend of butyl- and phenyl-tin contamination in organisms of the Lagoon of Venice (1999-2003).

In the period 1999-2003 a monitoring study on the accumulation of organotin compounds in edible organisms in the Lagoon of Venice was conducted. Butyl and Phenyl derivatives were determined in pooled samples of Mytilus galloprovincialis and Tapes spp. with the aims of assessing organotin contamination in the Lagoon of Venice in the period just preceding their ban in Europe, monitoring the concentrations in organisms with a high commercial use, evaluating a potential hazard for human health due to seafood and identifying the possible contamination sources. Sampling stations (up to 20) were distributed around the Lagoon and particularly concentrated in the area close to the town of Chioggia. Significantly higher (analysis of variance (ANOVA), p < 0.05) tributyltin (TBT) concentrations were found in mussels (from 38 +/- 8 to 6,666 +/- 1,333 microg kg(-1) d.w., as TBT(+)), than in clams (from 6 +/- 1 to 2,256 +/- 451 microg kg(-1) d.w., as TBT(+)). During the 3 years of the survey no increase in average concentrations of the butyltin compounds (tributyltin (TBT) + dibutyltin (DBT) + monobutyltin (MBT)) was observed (ANOVA, p > 0.05) in either species. Furthermore, by analyzing the entire data set, it is evident that most stations show analogous concentrations in the 3 years for both species, whereas few have anomalously higher concentrations. If organotin concentrations in specimens from some sites are compared with the Tolerable Average Residue Level, a possible risk for human health must be considered.

Assessment of organic chlorinated compound removal from aqueous matrices by adsorption on activated carbon.

Adsorption on activated carbon is currently the most frequently used technology to remove organic chlorinated pollutants from wastewaters. The present study examines the ability of five commercially available types of activated carbon to remove organic chlorinated compounds from the effluent of a chemical plant. The various types were tested on the basis of Freundlich adsorption isotherms for 14 pure organic chlorinated compounds, of molecular weight ranging from that of dichloromethane (MW=84.93 gmol(-1)) to hexachlorobenzene (MW=284.78 gmol(-1)). The best was selected and used in a laboratory fixed-bed column to assess its removal efficiency with respect to the tested organic chlorinated compounds. Removal efficiency was always higher than 90%. These results provide information necessary to optimize scale-up from the pilot plant to the real one.

Heavy metal contamination in the seaweeds of the Venice lagoon.

The concentrations of heavy metals (Fe, Zn, Cu, Cd, Ni, Pb, Cr, As) were determined in seven seaweeds of environmental and commercial relevance (Ulva rigida C. Ag., Gracilaria gracilis (Stackhouse) Steentoft, L. Irvine and Farnham, Porphyra leucosticta Thuret, Grateloupia doryphora (Montagne) Howe., Undaria pinnatifida (Harv.) Suringar, Fucus virsoides J. Agardh, Cystoseira barbata (Good. et Wood.) Ag.) collected in four sampling sites in the lagoon of Venice, in spring and autumn 1999. Metals were extracted using hot concentrated acids in a Microwave Digestion Rotor and analysed by absorption spectrophotometry using a flame mode for Fe and Zn and a graphite furnace for Pb, Cr, Cd, Cu, Ni and As. High contamination levels, especially for Pb, were detected in Ulva and to a lesser extent in Gracilaria. Brown seaweeds, especially Cystoseira was highly contaminated by As. The least contaminated genera with all metals except As were Porphyra and Undaria. A concentration decrease for Zn and Cd was observed from the inner parts of the central lagoon, close to the industrial district, towards the lagoon openings to the sea.

Chemical analyses of heavy metal contamination in sediments of the Venice Lagoon and toxicological implications.

Heavy metals are extracted from sediments using 1 M HCl; then, solutions are neutralised with 1 M NaOH, to fit the conditions suitable for the Vibrio Fischeri test. In the neutralised solutions different percentages of initial metal concentration are present, depending on the individual solubilities. The chemical investigation of the metal fraction extracted from the sediment with this procedure and the different metal bioavailability depending on the presence of natural complexing agents are the subject of this work. The results obtained confirm the good agreement between heavy metal fraction extracted using 1 M HCl and the anthropogenic component in the sediment. The use of voltammetric techniques, and the addition of low molecular weight humic acids into extracts show the ability of natural complexing agents in affecting heavy metal bioavailability and toxicity.

Macrofauna impact on Ulva rigida C. Ag. production and relationship with environmental variables in the lagoon of Venice.

The grazing pressure of the macrofaunal invertebrates associated with the biomass of Ulva rigida in the Venice lagoon, their species composition and relationship with environmental variables have been studied. Fifteen sampling campaigns were carried out during different seasons both in the central basin of the lagoon, dominated by macroalgae (especially U. rigida C. Ag.) and in the southern basin, prevalently populated by seagrasses (especially Zostera marina L.). Replicate experiments were conducted in the field by exposing Ulva fronds in net cages of 10 and 1 mm (control) mesh-sizes to allow or prevent grazer entrance. The grazing pressure was determined as Ulva growth rate difference in the cages. In the absence of invertebrate herbivores, Ulva exhibited per cent relative growth rates (%RGRs) ranging from 1.5 to 9.5% day(-1), whereas in their presence the %RGRs were significantly lower (from -2.5 to 3.4% day(-1)) and frequently negative, especially in the station dominated by macroalgae. In this area, peak grazing rates and macrofauna biomasses of up to 8.6% day(-1) and 1,480 g m(-2) fwt (84.4 ash-free dry weight), respectively, were found. On the whole, during in field experiments in the Ulva-dominated station, herbivores removed an amount of biomass whose percentage ranged from 59 to 165% (mean: 103%) of the biomass yield (grazers excluded) found in the cages. These results suggest the possibility that grazers could act as an important factor affecting Ulva production in the Venice lagoon. Macrofauna populations were analysed by means of multivaliate techniques applied to biological variables only and biological and environmental variables together. Data of individual abundance, after a log(x + 1) transformation and the calculation of the Bray-Curtis matrix, were classified using the Cluster Analysis and ordinated by means of the Non-Metric Multidimensional Scaling (MDS) technique, in accordance with the strategies used in the study of multispecies distributions. Finally, biological and environmental variables were analysed together by means of correlation matrices and the Principal Component Analysis.

Environmental and biological monitoring of occupational exposure to organic micropollutants in gasoline.

An exposure risk assessment of workers in a refinery production unit was undertaken. Gasoline and its main components were investigated through environmental and biological monitoring. Measured variables were environmental benzene, toluene, pentane and hexane; benzene and toluene in blood and urine; tt-MA (metabolite of benzene) in urine. Multivariate statistical analysis of the data showed that worker's exposure to the above substances fell within the limits specified by organisations such as ACGIH. Also, biological values complied with reference values (RV) for non-occupationally-exposed population. Different values of biological variables were determined by separating smokers from non-smokers: smokers had hematic and urinary benzene values significantly higher than non-smokers. During a 3-yr sampling, it was possible to identify a significant decrease of benzene in the workplace air and of hematic benzene for non-smokers. The most exposed department, one in which tank-lorries were loaded, needs further investigation and extended monitoring.

Correlation between inorganic (heavy metals) and organic (PCBs and PAHs) micropollutant concentrations during sewage sludge composting processes.

The nature and congener composition of PCBs and PAHs present in sewage sludge composting processes was investigated. These studies included analysis of the most significant process parameters (such as pH, temperature, weight percentage variation) and in addition heavy metals whose typical composting speciation and behaviour were also considered in order to better understand organic compound time profiles. The significant correlation found between Pb, Cd, Cu and PCBs and between PAHs and Hg implies that quite a strong adsorption of PCBs onto organic matter takes place and also provides evidence for the volatilisation of PAHs. Chemical characteristics of inorganic species and organic compounds are summarised to account for the observed correlation and time trend profiles. Moreover, single congener concentrations demonstrate that the number of Cl substituents for PCBs and condensed benzene rings for PAHs determine to what extent they can be broken down for biodegradation and removed through volatilisation respectively.

Micropollutants and organic carbon concentrations in surface and deep sediments in the Tunisian coast near the city of Sousse.

A radioactive tracer was used to map the plume of the effluent of a municipal water treatment plant located on the Tunisian coast, close to the city of Sousse. A sampling campaign was programmed on the basis of the radioactivity distribution. The extent of sediment contamination was investigated to determine the impact of the plant effluent. Organic carbon and organic micropollutants (PCBs and chlorinated pesticides) were analysed on resuspendable particulate matter, on grab and core sediments. The area distributions of different compounds analysed were studied and relationships were investigated between radioactivity and organic carbon and micropollutant data. The study shows that sludge particles are deposited and accumulate in the zone south of the effluent outlet, contaminating sediments. Good correlations were found which demonstrate the efficiency of the technique used to plan the sampling and the link between organic carbon and organic micropollutants.

Biochemical and histochemical responses to environmental contaminants in clam, Tapes philippinarum, transplanted to different polluted areas of Venice Lagoon, Italy.

In this study the clam, Tapes philippinarum, a filter-feeding bivalve living in soft bottoms, was used to investigate the water/sediment pollution in Venice Lagoon (Venice, Italy), a heavily urbanised and industrialised area. To this end, clams collected from indigenous populations in a clean farming area (Val Dogà) were transplanted into a relatively low contaminated site (Palude della Rosa) and in a heavily polluted area (Porto Marghera), for 5 weeks. A range of possible induced stress indices were measured, on the basis of potential toxicity mechanisms, including specific enzymatic activities [Bap hydroxylase and NADPH cytochrome c reductase, superoxide dismutase, catalase, glutathione peroxidase and propionaldehyde dehydrogenase (PDH)] and general cellular responses (lysosomal latency). Moreover, chemical analyses (polychlorinated biphenyls, polycyclic aromatic hydrocarbon, DDTs) were carried out on sediments and animal tissues at the beginning and end of the transplantation experiments. The chemical results show an active bio-accumulation activity from sediment in clams translocated to the most polluted area. Correspondingly, biological data indicate marked effects on PDH activity and latency in T. philippinarum from the same site. In contrast, no similar pattern has been observed in the other considered indices, possibly due to antagonistic effects of the complex contaminant mixture present in the environment.

Time trend of PCB concentrations in surface sediments from a hypertrophic, macroalgae populated area of the lagoon of Venice.

The concentrations of polychlorinated biphenyls have been determined over a period of 1 year in surface sediments sampled monthly and semi-monthly in the lagoon of Venice. At the sampling station, due to the poor water circulation and an over-abundance of nutrients, macroalgae thrive in spring-summer and standing crops greater than 12 kg m-2 were determined. As a consequence of rapid algal decomposition, sediment PCB concentrations were observed to increase. In particular, on occasions when anoxia occurred at the end of July and all the biomass had decayed, PCB concentrations increased by more than one order of magnitude. In March, when macroalgae started to grow, concentrations were 13 ng g-1 (dry wt); in July-August they exceeded 100 ng g-1. The sediment PCB concentrations were restored to the previous values after algal biomass became negligible, in November. Concentrations of PCBs in young algae fronds were 27 +/- 12 ng g-1, and 121 +/- 4 ng g-1 in older fronds.

Polychlorinated biphenyl pollution caused by resuspension of surface sediments in the lagoon of Venice.

A mechanical device was used to reproduce in the laboratory the sediment resuspension caused by tidal currents and wind waves in the lagoon of Venice. Shear stresses comparable to those observed in the field were applied to the sediment surface. Series of experiments were run at 6.6 and 9.0 dyn/cm2. The concentration of polychlorinated biphenyls (PCBs) were determined in the sediments and resuspended particulate matter by means of gas chromatographic techniques. At the two different stresses, particulate matter with different grain size and different concentrations of PCBs was resuspended. However, no significant differences were observed in the amounts of PCBs mobilized per litre of water. In fact, by increasing the applied stress, coarser particulate matter was resuspended with a lower concentration of PCBs per unit of dry weight.