POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

A comparison of results from two test methods for assessing the toxicity of aminotriazole to Selenastrum capricornutum

Two different test methods for assessing the toxicity of aminotriazole to Selenastrum capricornutum are compared. Growth medium composition is demonstrated to have a significant effect on the toxicity of aminotriazole.     

Atmospheric bulk deposition to the lagoon of Venice Part I. Fluxes of metals, nutrients and organic contaminants

First available data on atmospheric fall-out were provided by sampling monthly bulk depositions in four sites inside the Lagoon of Venice (550 km2). Sampling was carried out monthly during the period July 1998-July 1999, in one site near an industrial area (Porto Marghera; site D), another site in the city of Venice (site A), and the remaining two in the southern- and northernmost ends of the Lagoon (Valle Figheri, site C; Valle Dogà site B). The following determinations were carried out for each samples: pH, conductivity, grain-size, particulate load, and dissolved nutrients (N, P). Samples were then subdivided into soluble and insoluble fractions, and Al, Ca, Na, K, Mg, Si, Mn, Fe, Zn, Ni, Cr, Cu, Pb, Cd, As, Hg, Ti, V, S, P, Se and Sb were analysed on both fractions. Total organic micropollutants (PAH, PCB, HCB, DDT, PCDD/F) were measured. As regards particle size distribution, there was great variability among sampling sites. The percentage of the < or =2 microm grain-size fraction was higher in the southern and northern ends of the Lagoon. Small differences were found among sites for major elements, whereas higher variability was observed for inorganic and organic micropollutants, with standard deviations between 20% and 60% of the fluxes measured. Major differences in annual fluxes between the most polluted sites (mostly D and A) and background (site B) were seen for Cd (0.26 vs. 0.06 mg m(-2) year(-1)), Hg (41 vs. 15 microg m(-2) year(-1)), PCB ( approximately 2500 vs. approximately 500 ng m(-2) year(-1)) and HCB ( approximately 8000 vs. approximately 1000 ng m(-2) year(-1)). Comparisons with previous data, collected in the periods 1993-1994 and 1995-1997, were only available for a few trace metals. A definite decline in the annual Pb flux in the city of Venice was detected, from 18 to 13 mg m(-2) in 1996/1997 and 1995/1996 respectively, to approximately 5 mg m(-2) in the present study. Total annual deposition was calculated by means of two different methods, which gave very similar results: (i) the mean value of deposition in the four sites was multiplied by lagoon area (550 km2); (ii) the monthly rain isopleths were combined to normalize deposition values. The figures are: 15-34 kg of Hg and Sb, approximately 200 kg of As, approximately 100 kg of Cd and PAH, 0.7-1.3 tons of Cr, Ni and V, more than 2 tons of Cu and Pb, 17 of Zn, 55 of total P, approximately 200 of Al, and 3900 of DIN. Total fluxes of organics inside the lagoon were: PAH approximately 100 kg; HCB approximately 1 kg; DDT approximately 0.4 kg. PCB and PCDD/F fluxes were approximately 500 g and approximately 10 g, corresponding respectively to 0.1 and 0.4 g I-TE. The correlations between fluxes of inorganic micropollutants and grain-size were significant. Multivariate statistical analysis was applied to investigate more accurately relationships between the insoluble and dissolved fractions of inorganic micropollutants and grain-size fractions. In particular, significant correlations were highlighted between the dissolved fraction of As and the < or =1 mum particle size fraction. Relations between levels of SigmaPCDDF, SigmaPCDD, PCB and PAH congeners and grain-size revealed significant correlation coefficients for the remote sites (B, C), and none in the urban and industrial sites (A, D). In particular, significant correlations were highlighted between SigmaPCDDF, SigmaPCDD and particle size fraction < or =2 mum, and between benzo(a)pyrene and PCB 167 and particle size fraction 4-8 mum.     

The composition and relationships between trace element levels in inhalable atmospheric particles (PM10) and in leaves of Nerium oleander L. and Lantana camara L

In order to evaluate the composition of inhalable atmospheric particles and to study the relationship between trace element levels in PM10 and in leaves of two plant species, the amount of Ba, Cu, Fe, Mn, Pb, Ti and V were analysed in PM10 and in Nerium oleander L. and Lantana camara L. leaves from two sites in the city of Seville and one remote control site. In PM10, the Cu and Fe content was significantly lower (p<0.05) in the control site than in the other sites. No correlations between leaf content and air content were found for the elements in L. camara. On the contrary, positive and significant correlations (p<0.05) were found between leaf content of N. oleander and PM10 content for Cu and Fe. The data suggest that N. oleander can be used in atmospheric biomonitoring studies, because it is especially useful for Cu and Fe, N. oleander being a better indicator than L. camara.     

Chemical defense: incorporation of diet-derived pyrrolizidine alkaloid into the integumental scales of a moth (<Emphasis Type="Italic">Utetheisa ornatrix</Emphasis>)

Summary. Evidence is presented that pyrrolizidine alkaloid acquired by Utetheisa ornatrix (Lepidoptera, Arctiidae) as a larva from Crotalaria foodplants is incorporated in part into the scales of the adult. A single forewing of a male or female moth may contain in the order of 6 to 13 g monocrotaline in its scale cover or about 1 to 2% of the moths systemic monocrotaline content. Based on estimates of the number of scales per forewing, the monocrotaline content of individual scales is calculated to be in the order of 0.1 and 0.2 ng monocrotaline per male and female scale, respectively. This amounts to concentrations of about 1 and 3%, values roughly at a par with the average systemic concentration (0.5-0.6%) previously determined for monocrotaline in Utetheisa. It is argued that the presence of pyrrolizidine alkaloid in the moths scale coating could account for the promptness with which adult Utetheisa are rejected by spiders. It is suggested further that chemical impregnation of scales with substances deterrent to predators may be more widespread among insects than generally assumed.     

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

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

Precopulatory assessment of male quality in an arctiid moth (Utetheisa ornatrix): hydroxydanaidal is the only criterion of choice

Females of the moth Utetheisa ornatrix (Lepidoptera: Arctiidae) mate preferentially with males that excel in three quantitatively correlated attributes: body mass, systemic content of defensive pyrrolizidine alkaloid (derived from the larval diet), and glandular content of the courtship pheromone hydroxydanaidal (derived from the alkaloid). By so choosing, the females obtain direct phenotypic benefits (alkaloid and nutrient received with the spermatophore), and indirect genetic benefits (genes for large size, a heritable trait). We asked whether the female appraises the courting male on the basis of all three attributes, or whether, as had been postulated, she does so on the basis of the intensity of the pheromonal scent alone. We present data indicating that male possession of hydroxydanaidal is indeed the sole criterion of choice. Females fail to differentiate between males that differ in body mass or alkaloid content if the males lack hydroxydanaidal, but choose between males that are size-matched and alkaloid-free if one of the males has been experimentally endowed with hydroxydanaidal. We show moreover that females are able to differentiate between males that contain unequal quantities of hydroxydanaidal. Females abide by these criteria whether or not they themselves contain alkaloid. Their choice was also unaffected by whether they were confined singly with 2 males in small mating chambers, or were in groups of 10 with 20 males in large flight cages.     

Fire risk management system for safe operation of large atmospheric storage tanks

This paper has been prepared by its authors to show the benefits coming from the application of the fire risk assessment methodology prepared by the “LastFire^© Project” group of experts. Now a days this methodology seems to be very effective to face the fire risk connected with large atmospheric storage tanks. It has been developed during the period 1997–2005 the HSE & operations experts from experts 16 worldwide operating oil companies. The authors, by “ad hoc” created software package, show the benefit coming from the applications of the LastFire^© methodology and how, from this, using the methodology and the supporting tad, realize a coherent fire strategy in the form of a Fire Risk Management System. Same workflow could also be extended to the issues connected with other problems related with large atmospheric tanks storing hydrocarbons, such as environmental impact by soil pollution, to create a common frame walk of assessment not can be shared with authorities as well. The proposed methodology, moving from the original project, sets as an effective “Fire Hazard Management Approach” in line with the most recent trends (even enforced by the regulations) shared at international levels, that propose the integration of risk assessment with prevention and protection measures selection based on achieved risk reduction, costs, time needed, etc.     

Assessment of airborne heavy metal pollution by aboveground plant parts

Italian stone pine (Pinus pinea L.) and oleander (Nerium oleander L.) leaves, bark and wood samples were collected at different sites around an industrial area (Huelva, SW Spain) and compared with samples of the same species from a background site. Samples were analysed with respect to the following pollutants: Al, Ba, Cr, Cu, Fe and Pb by ICP-AES. The suitability of different plant parts as biomonitors of pollution was investigated. In pine samples from the polluted sites the ratio of concentrations between bark and wood was high for Al, Ba, Cu and Fe, whereas no differences were found in samples from the unpolluted area. No differences were detected in oleander for the same ratio. In the oleander species, the ratio between leaves and wood concentration allowed to distinguish between control and polluted sites. The ratio of the concentration between leaves and wood was elevated for Al, Ba and Fe in pine samples from the polluted sites. The ratio of the concentration in bark or leaves to their concentration in wood might be useful to detect inorganic atmospheric pollutants.