Potential sources and meteorological factors affecting PM<Subscript>2.5</Subscript>-bound polycyclic aromatic hydrocarbon levels in six main cities of northeastern Italy: an assessment of the related carcinogenic and mutagenic risks

A yearlong sampling campaign (2012–2013) was conducted in six major cities of the Veneto region to investigate the spatial-temporal trends and the factors affecting the polycyclic aromatic hydrocarbon (PAHs) variations and identify the local sources. Sixty samples per city were collected for analyses in every alternate month (April, June, August, October, December, and February): 10 samples per sampling site in 10 consecutive days of the months selected. Samples were ultrasonically extracted with acetonitrile and processed through high-performance liquid chromatography. Total Σ-PAH concentrations ranged from 0.19 to 70.4 ng m^?3 with a mean concentration of 11.5 ng m^?3. The mean benzo[a]pyrene (BaP) concentration reached 2.0 ng m^?3, which is two-times higher than the limit set by the European Union. BaP contributed for 17.4% to the total concentration of PAHs, which showed the same pattern across the region with maxima during cold months and minima in the warm period. In this study, PAHs showed an inverse relationship with temperature, solar radiation, wind speed, and ozone. According to this study, biomass burning for household heating and cooking, followed by gaseous PAHs absorption on particles due to low atmospheric temperature, were the main reasons for increasing PAHs concentration in winter. Health risk, evaluated as lifetime lung cancer risk (LCR), showed a potential carcinogenic risk from the airborne BaP_TEQ six-fold higher in the cold season than in the warm one. Diagnostic ratios and conditional probability functions were used to locate the sources, and results confirmed that local emission, overall domestic heating, and road transport exhausts were responsible for higher concentration rates of PAHs as well as of PM_2.5.     

ENVIRONMENTAL IMPACT EVALUATION OF HAZARDOUS WASTE DISPOSAL IN LAND1

Since the publication of Rachel Carson's Silent Spring in 1962 there has been a rapidly growing public concern over widespread contamination of the environment with hazardous wastes. In recent years scientific findings on the ecological effects of various hazardous substances have posed several important questions. What exactly are hazardous wastes? Can these substances be disposed of in a technically feasible, economical, and safe way with assurance that they have been permanently eliminated from the ecosystem? What compositional alterations or movements of the hazardous wastes occur in water, soil, or air systems? What effect will these wastes have on the water, soil, or air systems? What effect will these wastes have on the water, soil, or air properties? Consequently, a University of Louisville study has developed a relevant definition of hazardous wastes for the Environmental Engineering profession together with priority of concern rating systems to delineate the degree of environmental impact imposed on a total ecosystem by a hazardous waste and the feasibility of disposing of hazardous substances at specific landfill sites. It is felt that refinements of the priority of concern rating systems offered here may provide a sound basis from which procedural decisions may be structured to establish future national hazardous waste disposal sites.     

The changing state of contamination in the Lagoon of Venice. Part 1: organic pollutants

The Lagoon of Venice is a transitional environment suffering from industrial, urban and agricultural impact. Recently the mechanical clam fishing, preventing a regular deposition of sediments has made sampling of cores suitable for radiodating very problematic. Therefore, in this study, in order to assess temporal and spatial trends of contamination, the same sampling scheme was repeated three times over a 12-year period. The concentrations of PCBs, PAHs and organochlorine pesticides were measured in the uppermost 5 cm of sediments collected in 25 sites in the central portion of the lagoon during three campaigns conducted in 1987, 1993 and 1998. Analytical results, validated statistically, indicated that, while PCB and pesticide concentrations tend to decrease during the considered period of time, PAH do not, showing that the input rate of these compounds to the lagoon environment is still important. A spatial trend of pollution was also found in the lagoon for PCBs and pesticides, which decrease from the sources, namely the industrial zone and the mouths of rivers, to areas closer to the sea: a reduction up to 80% and 90%, respectively, was monitored. PAH contamination, originating chiefly from incomplete combustion of fossil fuels, as inferred from ratios of congeners, was mainly located around the historical center of Venice, where most of the boat traffic is concentrated and has an increasing trend.     

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.     

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.     

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.     

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.     

Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation

Sediment samples were collected in the Gulf of Gdańsk, and the Vistula and Szczecin Lagoons—all located in the coastal zone of the Southern Baltic Sea—just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g^?1 d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdańsk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdańsk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.     

The changing state of contamination in the Lagoon of Venice. Part 2: heavy metals

In order to verify whether pollution is increasing or decreasing, in 25 locations uniformly distributed in the central part of the Lagoon of Venice, a transitional environment suffering from man's urban and industrial activities, the same sampling scheme was repeated three times (in 1987, 1993 and 1998) over a 12-year period during which the lagoonal environment underwent substantial changes. Superficial sediments were sampled and analysed for heavy metals and total organic carbon contents, grain size and density. In general heavy metal contents were found to be correlated, with concentrations above the background level, e.g., for Hg, a concentration factor of 24 was observed in 1987. A temporal decrease in concentrations was observed for most of the metals. Detailed analysis on a smaller spatial scale showed that contamination significantly decreases from the inner border of the lagoon seawards, as highlighted in contour maps. The role of the Porto Marghera industrial zone as a source of pollutants at the border of the Lagoon was confirmed. The decrease in contamination could not be attributed only to a decrease in the intensity of sources, but also to erosion processes, worsened by intensive harvesting of clams with hydraulic dredges.