The use of phosphonates in agriculture. Chemical, biological properties and legislative issues.

The Phosphorus (III) derivatives, named Phosphonates, include congeners with properties as fungicides that are effective in controlling Oomycetes. Examples are organic compounds like Fosetyl-Al [Aluminium tris-(ethylphosphonate)] and salts formed with the anion of phosphonic acid [(OH)2HPO] and Potassium, Sodium and Ammonium cations. According to IUPAC, the correct nomenclature for these compounds is "phosphonates", but in common language and scientific literature they are often named "phosphites", creating ambiguity. The European legislation restricts the use of phosphonates, with the ban for application in organic agriculture. However, phosphonate residues were detected in some organic products due to their addition to fertilizers allowed in organic agriculture. The legitimacy of this addition is controversial, as it is not evident if phosphonates have also a nutritional role in addition to their fungicidal properties. The new European Directive EU 1009/2019 resolves the problem by banning the phosphonates addition to fertilizers and placing a limit of 0.5% by mass for unintentional addition. However, an official method is not available for phosphonates determination in fertilizers and approval by the European Committee for Standardization (CEN) is necessary in a short time. This review presents an overview about the chemical, biological, analytical and legislative aspects of phosphonates and aims at providing: clarity on the correct nomenclature to avoid misunderstandings; the evaluation of phosphonates properties with the absence of a nutritional role, justifying the ban on adding to fertilizers; a summary of analytical techniques that could be considered by CEN to complete the analytical background for the agricultural use of phosphonates.

Hybrid multiple-site mass closure and source apportionment of PM2.5 and aerosol acidity at major cities in the Po Valley.

This study investigates the major chemical components, particle-bound water content, acidity (pH), and major potential sources of PM2.5 in major cities (Belluno, Conegliano, Vicenza, Mestre, Padua, and Rovigo) in the eastern end of the Po Valley. The measured PM2.5 mass was reconstructed using a multiple-site hybrid chemical mass closure approach that also accounts for aerosol inorganic water content (AWC) estimated by the ISORROPIA-II model. Annually, organic matter accounted for 31-45% of the PM2.5 at all sites, followed by nitrate (10-19%), crustal material (10-14%), sulfate (8-10%), ammonium (5-9%), elemental carbon (4-7%), other inorganic ions (3-4%), and trace elements (0.2-0.3%). Water represented 7-10% of measured PM2.5. The ambient aerosol pH varied from 1.5 to 4.5 with lower values in summer (average in all sites 2.2 ± 0.3) and higher in winter (3.9 ± 0.3). Six major PM2.5 sources were quantitatively identified with multiple-site positive matrix factorization: secondary sulfate (34% of PM2.5), secondary nitrate (30%), biomass burning (17%), traffic (11%), re-suspended dust (5%), and fossil fuel combustion (3%). Biomass burning accounted for ~90% of total PAHs. Inorganic aerosol acidity was driven primarily by secondary sulfate, fossil fuel combustion (decreasing pH), secondary nitrate, and biomass burning (increasing pH). Secondary nitrate was the primary driver of the inorganic AWC variability. A concentration-weighted trajectory (multiple-site) analysis was used to identify potential source areas for the various factors and modeled aerosol acidity. Eastern and Central Europe were the main source areas of secondary species. Less acidic aerosol was associated with air masses originating from Northern Europe owing to the elevated presence of the nitrate factor. More acidic particles were observed for air masses traversing the Po Valley and the Mediterranean, possibly due to the higher contributions of fossil fuel combustion factor and the loss of nitric acid due to its interaction with coarse sea-salt particles.

Potential sources and meteorological factors affecting PM2.5-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 BaPTEQ 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 PM2.5.

A procedure to evaluate the factors determining the elemental composition of PM2.5. Case study: the Veneto region (northeastern Italy).

The Po Valley is one of the most important hot spots in Europe for air pollution. Morphological features and anthropogenic pressures lead to frequent breaching of air quality standards and to high-pollution episodes in an ~46 × 103-km2-wide alluvial lowland. Therefore, it is increasingly important to study the air quality in a wide geographical scale to better implement possible and successful mitigation measures. The Veneto region lies in the eastern part of the Po Valley and the elemental composition of PM has been mainly studied in the Venice area, whereas scarce data are available for the remaining territory of the region. In this study, the elemental composition of PM2.5 was investigated over 1 year (2012-2013) at six major cities of the Veneto region. Samples were analyzed for 16 elements (Ca, Al, Fe, S, K, Mg, Ti, Mn, Zn, Ba, As, Ni, Pb, Sb, V, and Cu), and results were processed to investigate spatial and seasonal variations, the influence of meteorological factors, and the most probable sources by using a procedure based on (i) elemental ratios (Cu/Sb, Cu/Zn, Cu/Pb, Mn/V, V/Ni, and Zn/Pb), (ii) cluster analysis on wind data, and (iii) conditional probability function (CPF). The percentage of elements in PM2.5 ranged between 11 and 20%, and Ca and S were the most abundant elements in the region. Typical seasonal variations and similar trends were exhibited by each element, especially in the lowland. Some elements such as Zn, K, Mn, Pb, and Sb were found at high concentrations during the cold period. However, no similar dispersion processes were observed throughout the region, and their concentrations were mostly depending on individual local sources. In the alpine and foothill parts of the region, lower concentrations were recorded with respect to the Po Valley cities, which resulted enriched of most of the elements considered in this study. The cluster analysis on wind data and the CPF of the ratio-related sources demonstrated that a widespread pollution condition exists in the region, apart from the coastal area. However, specific directions (e.g., a link with high-traffic roads, industrial areas, and airports) resulted the most probable explanation for each ratio-related source. In addition, the Veneto region hosts one of the most important Mediterranean ports for the cruise sector (Venice harbor), and its impact was previously demonstrated in the historical city center. In this study, the impact of Venice shipping emissions was estimated to be 3.5% of PM2.5 in some particular days.

Estimation of local and external contributions of biomass burning to PM2.5 in an industrial zone included in a large urban settlement.

A total of 85 PM2.5 samples were collected at a site located in a large industrial zone (Porto Marghera, Venice, Italy) during a 1-year-long sampling campaign. Samples were analyzed to determine water-soluble inorganic ions, elemental and organic carbon, and levoglucosan, and results were processed to investigate the seasonal patterns, the relationship between the analyzed species, and the most probable sources by using a set of tools, including (i) conditional probability function (CPF), (ii) conditional bivariate probability function (CBPF), (iii) concentration weighted trajectory (CWT), and (iv) potential source contribution function (PSCF) analyses. Furthermore, the importance of biomass combustions to PM2.5 was also estimated. Average PM2.5 concentrations ranged between 54 and 16 µg m-3 in the cold and warm period, respectively. The mean value of total ions was 11 µg m-3 (range 1-46 µg m-3): The most abundant ion was nitrate with a share of 44 % followed by sulfate (29 %), ammonium (14 %), potassium (4 %), and chloride (4 %). Levoglucosan accounted for 1.2 % of the PM2.5 mass, and its concentration ranged from few ng m-3 in warm periods to 2.66 µg m-3 during winter. Average concentrations of levoglucosan during the cold period were higher than those found in other European urban sites. This result may indicate a great influence of biomass combustions on particulate matter pollution. Elemental and organic carbon (EC, OC) showed similar behavior, with the highest contributions during cold periods and lower during summer. The ratios between biomass burning indicators (K+, Cl-, NO3-, SO42-, levoglucosan, EC, and OC) were used as proxy for the biomass burning estimation, and the contribution to the OC and PM2.5 was also calculated by using the levoglucosan (LG)/OC and LG/PM2.5 ratios and was estimated to be 29 and 18 %, respectively.

Carbonaceous PM(2.5) and secondary organic aerosol across the Veneto region (NE Italy).

Organic and elemental carbon (OC-EC) were measured in 360 PM2.5 samples collected from April 2012 to February 2013 at six provinces in the Veneto region, to determine the factors affecting the carbonaceous aerosol variations. The 60 daily samples have been collected simultaneously in all sites during 10 consecutive days for 6 months (April, June, August, October, December and February). OC ranged from 0.98 to 22.34 µg/m(3), while the mean value was 5.5 µg/m(3), contributing 79% of total carbon. EC concentrations fluctuated from 0.19 to 11.90 µg/m(3) with an annual mean value of 1.31 µg/m(3) (19% of the total carbon). The monthly OC concentration gradually increased from April to December. The EC did not vary in accordance with OC. However the highest values for both parameters were recorded in the cold period. The mean OC/EC ratio is 4.54, which is higher than the values observed in most of the other European cities. The secondary organic carbon (SOC) contributed for 69% of the total OC and this was confirmed by both the approaches OC/EC minimum ratio and regression. The results show that OC, EC and SOC exhibited higher concentration during winter months in all measurement sites, suggesting that the stable atmosphere and lower mixing play important role for the accumulation of air pollutant and hasten the condensation or adsorption of volatile organic compounds over the Veneto region. Significant meteorological factors controlling OC and EC were investigated by fitting linear models and using a robust procedure based on weighted likelihood, suggesting that low wind speed and temperature favour accumulation of emissions from local sources. Conditional probability function and conditional bivariate probability function plots indicate that both biomass burning and vehicular traffic are probably the main local sources for carbonaceous particulate matter emissions in two selected cities.

The size distribution of chemical elements of atmospheric aerosol at a semi-rural coastal site in Venice (Italy). The role of atmospheric circulation.

The concentrations of selected elemental tracers were determined in the aerosol of a semi-rural coastal site near Venice (Italy). Size-segregated aerosol samples were collected using an 8-stage cascade impactor set at 15m above ground, during the cold season (late autumn and winter), when high levels of many pollutants are known to cause risks for human health. From the experimental data, information was extracted on potential pollutant sources by investigating the relationships between elements in the different size fractions. Moreover, an approach to highlight the importance of local atmospheric circulation and air mass origin in influencing the PM composition and fractional distribution is proposed. Anthropogenic elements are strongly inter-correlated in the submicrometric (<1 µm) (S, K, Mn, Cu, Fe and Zn) and intermediate mode (1-4 µm) (Mn, Cu, Zn, Ni) and their relationships highlight the presence of several sources (combustions, secondary aerosol, road traffic). In the intermediate mode, associations having geochemical significance exist between marine (Na, Cl and Mg) and crustal (Si, Mg, Ca, Al, Ti and K) elements. In the coarse mode (>4 µm) Fe and Zn are well correlated and are probably linked to tire and brake wear emissions. Regarding atmospheric circulation, results show increasing levels of elements related to pollution sources (S, K, Mn, Ni, Cu, Zn) when air masses come from Central and Eastern Europe direction and on the ground wind blows from NWN-N-NE (from mainland Venice). Low wind speed and high percentage of wind calm hours favor element accumulation in the submicrometric and intermediate modes. Furthermore, strong winds favor the formation of sea-spray and the increase of Si in the coarse mode due to the resuspension of sand fine particles.

Interannual heavy element and nutrient concentration trends in the top sediments of Venice Lagoon (Italy).

The elemental composition of surficial sediments of Venice Lagoon (Italy) in 1987, 1993, 1998 and 2003 were investigated. Zn and Cr concentrations resulted in higher than background levels, but only Cd and Hg were higher than legal quality standards (Italian Decree 2010/260 and Water Framework Directive 2000/60/EC). Contaminants with similar spatial distribution are sorted into three groups by means of correlation analysis: (i) As, Co, Cd, Cu, Fe, Pb, Zn; (ii) Ni, Cr; (iii) Hg. Interannual concentrations are compared by applying a factor analysis to the matrix of differences between subsequent samplings. A general decrease of heavy metal levels is observed from 1987 to 1993, whereas particularly high concentrations of Ni and Cr are recorded in 1998 as a consequence of intense clam fishing, subsequently mitigated by better prevention of illegal harvesting. Due to the major role played by anthropogenic sediment resuspension, bathymetric variations are also considered.

Thirteen years of air pollution hourly monitoring in a large city: potential sources, trends, cycles and effects of car-free days.

Thirteen air pollutant concentrations were measured hourly for 13 years (2000-2013) at an urban background site of a large city in the eastern Po Valley (Italy) and results were chemometrically analysed. The pollutant list includes CO, NO, NO2, NOx, O3, SO2, benzene, toluene, ethylbenzene, o-, m- and p-xylenes and PM10, all known or suspected of having adverse effects on human health. The hourly data were statistically processed to detect the long-term trends in relation to the changes in the emission scenarios occurred in the last decade. The most probable emission sources and atmospheric photochemical processes were investigated by analyzing the seasonal, weekly, diurnal cycles of pollutants and the lagged correlations amongst pollutants. The role of micro-meteorological factors upon the air quality was assessed by analyzing the relationships with key weather parameters, while the location of the potential sources was studied by matching atmospheric circulation and pollution data through bivariate polar plots and conditional probability functions. In addition, a new statistical procedure is presented and tested to analyze the periods when common mitigation measures were adopted in the city (e.g., the total stop of traffic and car-free days) and to evaluate their real effect upon the air quality. By providing direct information on the levels and trends of key pollutants, this study finally enables some general considerations about air pollution in an important hotspot of Southern Europe, the eastern Po Valley, where the levels of some key pollutants are still far from meeting the EC limit and target values. It may help policy-makers to take successful mitigation measures.

The PM2.5 chemical composition in an industrial zone included in a large urban settlement: main sources and local background.

Chemical analyses, receptor modeling and meteorological data were combined to determine the composition and sources of PM2.5 sampled daily in a large area in Italy characterized by a high number of heterogeneous industrial emissions and contiguous to a major urban center. The PM2.5 local background in the area, i.e. the common basic composition and concentrations of PM2.5, was determined. Factor analysis-multiple linear regression analysis (FA-MLRA) was used to identify and quantify the main PM sources. Groups of samples with similar source contributions were then sorted using cluster analysis. The potential source location and the influence of long range transport were investigated by using the conditional probability function (CPF) and the potential source contribution function (PSCF) respectively. On an annual basis, five sources of PM were found relevant. Industrial emissions accounted for 3% of PM mass, whereas the main contribution to PM was related to a combination of ammonium nitrate, combustion (54%) and road traffic (36%), mainly related to urban emissions. The PM2.5 background was estimated to account for 20 µg m(-3). It comprises contributions of 55% ammonium nitrate and combustion, 46% road traffic, 6% fossil fuel combustion and 3% industrial emissions. Source contributions are influenced by both local atmospheric circulation and regional transport.

The dark side of the tradition: the polluting effect of Epiphany folk fires in the eastern Po Valley (Italy).

In the Veneto Region (Po Valley, Northeastern Italy) on the eve of Epiphany, an important religious celebration, during the night between January 5th and 6th thousands of folk fires traditionally burn wooden material. The object of this study is to characterize the 2013 episode, by monitoring the effects on the air quality in the region's lowlands. The daily concentrations of PM2.5 and PM10 exceeded 250 and 300 µg m(-3), respectively and the PM10 hourly values were above 600 µg m(-3) in many sites. The levels of total carbon, major inorganic ions, polycyclic aromatic hydrocarbons and biomass burning tracers (levoglucosan and K(+)) were measured in 84 samples of PM10 and 38 of PM2.5 collected at 32 sites between January 4th and 7th. Total carbon ranged from 11 µg m(-3) before the pollution episode to 131 µg m(-3) a day afterwards, K(+) from 0.6 to 5.1µg m(-3), benzo(a)pyrene from 2 to 23 ng m(-3), and levoglucosan from 0.5 to 8.3 µg m(-3). The dispersion of the particulate matter was traced by analyzing the levels of PM10 and PM2.5 in 133 and 51 sites, respectively, in the Veneto and neighboring regions. In addition to biomass burning the formation of secondary inorganic aerosol was revealed to be a key factor on a multivariate statistical data processing. By providing direct information on the effects of an intense and widespread biomass burning episode in the Po Valley, this study also enables some general considerations on biomass burning practices.

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 Gdansk, 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 Gdansk 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 Gdansk (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.

Using a photochemical model to assess the horizontal, vertical and time distribution of PM(2.5) in a complex area: relationships between the regional and local sources and the meteorological conditions.

A photochemical transport model has been implemented to assess the PM(2.5) spatial and temporal distribution in Venice-Mestre. This is a large city of the eastern Po Valley, which is recognized having among the highest levels of many air pollutants in Europe. This study is a first attempt to evaluate PM(2.5) distribution in such a complex ecosystem strongly affected by several different environments (the adjacent Alps, the lagoon and the sea) that create a spatial discontinuity of climate. Model performance was tested with experimental results. Samples have been collected in three sites representative of different emission characteristics. A second simulation was performed with clean boundary conditions to check the influence of the background concentrations on the study domain. Local and regional contributions were found to be strongly dependent on seasonal conditions and on local meteorology. A further analysis was conducted to predict the PM(2.5) distribution with respect to air mass movements. The non-homogeneity of surfaces affects the Planetary Boundary Layer (PBL) behavior. This consequently influences the vertical distribution of PM(2.5) especially during cold seasons and on occasion of particular meteorological events.

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.

Chemical analyses of spring waters and factor analysis to monitor the functioning of a karstic system. The role of precipitations regimen and anthropic pressures.

An approach is presented to study the functioning of a karstic massif and assess the adverse effects of the anthropogenic pressure by monitoring some water chemical and physical parameters of its main springs. The approach has been applied to the Sette Comuni Plateau (Veneto Region, Italy) hosting a well developed karstic system, whose aquifer presents high vulnerability and undergoes a relevant anthropogenic pressure. The Oliero springs, amongst the largest karstic springs in Europe, are the main water output of the plateau. Electrical conductivity, pH, dissolved O(2), hardness, alkalinity, chemical oxygen demand, total suspended solids, ionic species (NH(4)(+), NO(3)(-), NO(2)(-), PO(4)(3-), SO(4)(2-), Cl(-), F(-)), elements (Cr(III), Cr(VI), Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb), and some chlorinated solvents were monitored for one year. This study presents the application of a factor analysis on the water parameters enabling the identification of the dominant chemical and biological processes and pollution sources affecting the karstic system. Results show four factors which are interpreted as karstification, photosynthesis, storm flow pollution and anions. Finally, by associating metals, chemical oxygen demand and total suspended solids with the amount of rainfall in the 48 h before samplings, further detailed information to the fast response of the aquifer to precipitation events was detected and interpreted according to the factor analysis results. The proposed approach, by providing information on the functioning of the aquifer, may help the management of the karstic plateau and is easily adaptable to similar environments.

Periwinkle (Littorina littorea) as a sentinel species: a field study integrating chemical and biological analyses.

The gastropod Littorina littorea (common periwinkle) is an abundant and widespread North Atlantic species. The characteristic development of Intersex in L. littorea has been widely applied as a biomarker for tributyltin (TBT) contamination. Here, we assess the potential of L. littorea as a novel sentinel species for evaluating the sublethal effects in wild populations of widely distributed contaminants. We collected animals from six sites across the South coast of England. Tissue concentrations of polycyclic aromatic hydrocarbons (PAHs), organotin compounds (OTCs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were measured and compared with biomarkers of damage to DNA (Comet assay), lysosomal stability (NRR assay), and endocrine disruption (Intersex development). There was a strong correlation between DNA damage and PAH bioaccumulation (n=6, r=0.84, p<0.05), as well as that between Intersex development and OTC pollution (n=6, r=0.91, p<0.05). The relationship between PAH bioaccumulation and DNA strand breaks was nonlinear, highlighting the need to consider the role of adaptive mechanisms in the interpretation of field results. These results illustrate the potential use of periwinkles for monitoring a wide range of priority pollutants.

Organotin compounds in surface sediments from seaports on the Gulf of Gdansk (southern Baltic coast).

Sediment samples were collected in two Polish ports of international significance--the Port of Gdansk and the Port of Gdynia (Gulf of Gdansk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdansk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.

Characterization of PM10 sources in a coastal area near Venice (Italy): an application of factor-cluster analysis.

In this study a factor-cluster analysis (FCA) applied to chemical composition of atmospheric particulate matter was carried out. Relating specific wind data and back-trajectories to the daily samples grouped using FCA can be useful in atmospheric pollution studies to identify polluting sources and better interpret source apportionment results. The elemental composition and water soluble inorganic ions content of PM(10) were determined in a coastal site near Venice during the sea/land breeze season. From the factor analysis four sources were identified: mineral dust, road traffic, fossil fuels and marine aerosol. From a hierarchical cluster analysis, applied on the factor scores, samples with a similar source profile were grouped. Five clusters were identified: four with samples highly characterized by one identified source, one interpreted as general background pollution. Finally, by interpreting cluster results with wind direction data and back-trajectory analysis further detailed information was obtained on potential source locations and possible links between meteorological conditions and PM(10) chemical composition variations were detected. The proposed approach can be useful for air quality assessment studies and PM(10) reduction strategies.

Geochemical characterization of PM10 emitted by glass factories in Murano, Venice (Italy).

The atmosphere in Venice, like in other European cities, is influenced by complex PM(10) multi-emission sources with a net tendency to exceed the limits fixed by the directive 99/30/EC. This study investigated the composition of an ensemble of similar industrial sources, the Murano Glassmaking Factories (MGFs), and their influence on the Venice air quality, using a modelling approach, statistical analysis and geochemical considerations. Preliminary modelling simulations were conducted to select three sampling sites along the way of preferential transport of pollutants from source between February and April 2003. Subsequently, a sampling campaign was carried out in the same period of simulations. Concentrations of PM(10), eight major elements (Al, Ti, Ca, Mg, Na, K, Fe, Mn), 20 minor and trace elements (Li, V, Cr, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ru, Rh, Cd, Sb, Ba, Ce, Pt, Pb) and four PAHs (BaA, BbF, BkF, BaP) were quantified. The analytical results were statistically processed for exploring the relationships between inorganic elements and organic compounds, and results were interpreted using geochemical considerations. Results show a MGF component of PM(10) characterised by two different fingerprints: the first linked to glass raw material composition and the second mainly related to glass additives. Particularly, Cd, Se, As and Li preserve their ratios in all study area, and are interpreted as principal components of the MGF emissions. Other fingerprints can be traced to urban sources from the Venetian mainland.

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.