GC-MS analyses and chemometric processing to discriminate the local and long-distance sources of PAHs associated to atmospheric PM2.5.

PURPOSE: This study presents a procedure to differentiate the local and remote sources of particulate-bound polycyclic aromatic hydrocarbons (PAHs). METHODS: Data were collected during an extended PM(2.5) sampling campaign (2009-2010) carried out for 1 year in Venice-Mestre, Italy, at three stations with different emissive scenarios: urban, industrial, and semirural background. Diagnostic ratios and factor analysis were initially applied to point out the most probable sources. In a second step, the areal distribution of the identified sources was studied by applying the discriminant analysis on factor scores. Third, samples collected in days with similar atmospheric circulation patterns were grouped using a cluster analysis on wind data. Local contributions to PM(2.5) and PAHs were then assessed by interpreting cluster results with chemical data. RESULTS: Results evidenced that significantly lower levels of PM(2.5) and PAHs were found when faster winds changed air masses, whereas in presence of scarce ventilation, locally emitted pollutants were trapped and concentrations increased. This way, an estimation of pollutant loads due to local sources can be derived from data collected in days with similar wind patterns. Long-range contributions were detected by a cluster analysis on the air mass back-trajectories. Results revealed that PM(2.5) concentrations were relatively high when air masses had passed over the Po Valley. However, external sources do not significantly contribute to the PAHs load. CONCLUSIONS: The proposed procedure can be applied to other environments with minor modifications, and the obtained information can be useful to design local and national air pollution control strategies.

New implications in the use of imposex as a suitable tool for tributyltin contamination: experimental induction in Hexaplex trunculus (Gastropoda, Muricidae) with different stressors.

Imposex, i.e. the development of additional male sex organs (penis and/or vas deferens), in females of gonochorist marine and freshwater gastropods, is known to be caused by tributyltin (TBT), and it has been widely used as a biomonitoring tool in environmental surveys for TBT pollution assessment. In this study, we experimentally tested the potential to induce imposex by another endocrine disruptor (polychlorinated biphenyls [PCBs] mixture--Aroclor 1260). Adults of Hexaplex trunculus with low imposex level, coming from an Italian Marine Protected Area, were injected separately with different doses of tributyltin chloride (TBTCl) and Aroclor 1260. The compounds were dissolved in ethanol and the organisms were narcotised by immersion in MgCl(2) solution before injection. Before and after the experiment, butyltin compounds (BuTs) and PCB tissue concentrations were determined. A significant increase in imposex with respect to non-treated organisms was observed in all treatments, including artefact controls. No clear correlation was observed between BuTs and PCB tissue concentrations and indices of imposex incidence. Based on these results, no assumption can be formulated about PCB effect on imposex development. Nevertheless, they suggest that the imposex level increase, at least in H. trunculus, in laboratory conditions might not be caused by TBT only, but it would rather be a non-specific response to different stress stimuli.

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice.

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2+/-0.7-4.0+/-0.5; relative penis length: 6-47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs=43+/-14 ngSng(-1)w.) were significantly lower than in the other stations (range of average sum of BuTs: 101+/-22-217+/-27 ngSng(-1)d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r=0.95, n=8, p<0.05.

Organochlorine compounds (polychlorinated biphenyls and pesticides) and polycyclic aromatic hydrocarbons in populations of Hexaplex trunculus affected by imposex in the lagoon of Venice, Italy.

Concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides, and polycyclic aromatic hydrocarbons (PAHs) were measured in gastropods from the Lagoon of Venice, Italy. The visceral coil and the rest of the soft body of organisms (Hexaplex trunculus) sampled at two stations inside the lagoon and three stations on the seaward side were analyzed to evaluate their contamination levels. Preferential accumulation of PCBs and pesticides in the visceral coil (>80%) compared with the rest of the soft body was observed, whereas on average, PAHs showed no preferential partitioning. Differences between levels of organochlorine contaminants in the gastropods highlighted a gradient of pollution from the stations inside the lagoon (PCBs, 45-363 ng/g; pesticides, 4-51 ng/g) to the sea (PCBs, 13-131 ng/g; pesticides, 2-29 ng/g). The possible role of the three classes of contaminants, in addition to that of organotin compounds (OTCs), previously analyzed in the same samples, in causing one of the anatomic modifications because of imposex in this gastropod also was studied. A modeling approach by partial least squares (PLS) in latent variables was applied to explain the penis length of imposex-affected females with concentrations of organic pollutants. The synergistic role of PCBs, pesticides, and OTCs was evidenced, whereas the contribution of PAHs appeared to be very low.

Concentrations of organotin compounds and imposex in the gastropod Hexaplex trunculus from the Lagoon of Venice.

In four stations located close to the channels connecting the Lagoon of Venice with the Adriatic Sea (two inside the lagoon and two outside it), individuals of Hexaplex trunculus were collected in order to assess their contamination. Concentrations of some organotin compounds, i.e. tributyltin and triphenyltin with their di- and mono- substituted metabolites, were measured and endocrine disruption such as imposex (superimposition of male sexual characteristics on females of gonochoristic gastropods) was observed. Vas deferens sequence indexes (VDSI) of 4.1-4.9 were found in organisms from stations inside the lagoon, and 3.6-4.2 in the sea stations. Organotin derivatives were measured in both the visceral coil and the rest of the soft body of the organisms. Total concentrations of butyltin compounds ranged from 102 +/- 17 to 432 +/- 27 ng Sn g(-1) d.w. in the visceral coil, and from 96 +/- 24 to 297 +/- 107 ng Sn g(-1) d.w. in the rest of the soft body. Phenyltins were found at far lower concentrations, ranging from 8 +/- 1 to 41 +/- 3 ng Sn g(-1) d.w. (visceral coil) and from 0.25 to 32 +/- 22 ng Sn g(-1) d.w. (rest of soft body). The degree of imposex in female gastropods, evaluated from VDSI and penis lengths, was related to organotin contents in the soft body. In particular, female penis lengths were significantly correlated (r = 0.917 and r = 0.982, P<0.05) to tributyltin (TBT) contents and the sum of organotin compounds in organisms.