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Long-term time-series are a fundamental prerequisite to understand and detect climate shifts and trends. Understanding the complex interplay of changing ocean variables and the biological implication for marine ecosystems requires extensive data collection for monitoring and hypothesis testing and validation of modelling products. In marginal seas, such as Mediterranean Sea, there are still monitoring gaps, both in time and in space. To contribute filling these gaps, an extensive dataset of dissolved inorganic nutrients profiles (nitrate, NO3; phosphate, PO43−; and silicate, SiO2) have been collected between 2004 and 2017 in the Western Mediterranean Sea and subjected to quality control techniques to provide to the scientific community a publicly available, long-term, quality controlled, internally consistent biogeochemical data product. The database includes 870 stations of dissolved inorganic nutrients sampled during 24 cruises, including temperature and salinity. Details of the quality control (primary and secondary quality control) applied are reported. The data are available in PANGAEA (https://doi.org/10.1594/PANGAEA.904172, Belgacem et al. 2019).

This study investigates the major chemical components, particle-bound water content, acidity (pH), and major potential sources of PM2.5in major cities (Belluno, Conegliano, Vicenza, Mestre, Padua, and Rovigo) in the eastern end of the Po Valley. The measured PM2.5mass 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 PM2.5at 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 PM2.5sources 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.

Ocean life relies on the loads of dissolved inorganic nutrients (nitrate, phosphate and silicate) and other micro-nutrients into the euphotic layer. They fuel phytoplankton growth that maintains the equilibrium of the food web. Ocean circulation and physical processes continually drive the large -scale distribution of chemicals toward a homogeneous distribution (Williams and Follows, 2003). The biological and biochemical processes counteract this tendency. Therefore, describing nutrient dynamics is important to understand the overall ecosystem functioning.At global scale, most of the biogeochemical descriptions are based on model simulations and satellite data, since nutrient in situ observations are generally infrequent and not homogeneously distributed in space and time. Climatological mapping is often used to understand the biogeochemical state of the ocean representing monthly, seasonally or annual averaged fields.Within this context, the western Mediterranean Sea climatology (BGC-WMED) presented here is a product derived from in situ observations, derived from various data sources: in total, 2253 in-situ inorganic nutrient profiles over the period 1981-2017 have been used (Medar/MEDATLAS, Fichaut et al., 2003; the CNR-WMED biogeochemical dataset, Belgacem et al., 2020; SeaDataNet data product, https://www.seadatanet.org; Mediterranean Ocean Observing System for the Environment, MOOSE, http://www.moose-network.fr/).Annual mean gridded nutrient fields for the period 1981-2017, and sub-periods 1981-2004 and 2005-2017, on a horizontal 1/4° × 1/4° grid have been produced. The biogeochemical climatology is built on 19 depth levels and for the dissolved inorganic nutrients nitrate, phosphate and orthosilicate. To generate smooth and homogeneous interpolated fields, an advanced N-dimensional version of DIVA, DIVAnd v2.5.1 (Barth et al., 2014), which is based on the variational inverse method (VIM) (Brasseur et al., 1996), has been used.A sensitivity analysis was carried out to assess the comparability of the data product with the observational data. The BGC-WMED has then been compared to other available data products, i.e. the medBFM biogeochemical reanalysis and the biogeochemical component of WOA18.Keywords: Mediterranean Sea, climatology, inorganic nutrient, in situ observations.

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.

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.

This study investigates the major chemical components, particle-bound water content, acidity (pH), and major potential sources of PM

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 −, SO4 2−, 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.

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

The Veneto region lies in the eastern part of the Po Valley (Italy). This is one of the hotspots in Europe for air quality, where efforts to meet the European standard for PM2.5 according to current and future legislation have been generally unsuccessful. Recent data indicating that ammonium, nitrate and sulphate account for about one third of total PM2.5 mass show that secondary inorganic aerosol (SIA) plays a key role in the exceedence of the standards. A sampling campaign for PM2.5 was carried out simultaneously in six major cities (2012–2013). The water soluble inorganic ions were quantified and data processed to: (1) investigate the seasonal trends and the spatial variations of the ionic component of aerosol; (2) identify chemical characteristics at the regional-scale and (3) assess the potential effects of long-range transport using back-trajectory cluster analysis and concentration-weighted trajectory (CWT) models. Results indicated that PM2.5 and SIA ions have an increasing gradient in concentrations from North (mountain) to South (lowland) and from East (coastal) to West (more continental), whereas K+ and Ca2+ levels are quite uniformly distributed. Similar seasonal trends in PM2.5 and ions are seen across the region. Simultaneous daily changes were observed and interpreted as a consequence of similar emission sources, secondary pollutant generation and accumulation/removal processes. Sulphate and nitrate were not directly related to the concentrations of their precursor gases and were generally largely, but not completely, neutralised by ammonium. The clustering of back-trajectories and CWT demonstrate that the long-range movement of the air masses has a major impact upon PM2.5 and ion concentrations: an area spreading from Eastern to Central Europe was identified as a main potential source for most ions. The valley sites are also heavily influenced by local emissions in slow moving northerly air masses. Finally, two episodes of high nitrate levels were investigated to explain why some sites are experiencing much higher concentrations than others. This study identifies some key features in the generation of SIA in the Po Valley, demonstrating that SIA generation is a regional pollution phenomenon and mitigation policies are required at regional, national and even European scales.

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.

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.

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 × 10

This study investigates the chemical speciation of fine particulate matter (PM2.5) collected at three sites in the Venice area, eastern Po Valley (Italy). This area is one of the few hot spots left in Europe where levels of PM2.5 frequently breach EU target values and cause a serious risk for public health. Elemental composition, inorganic ions and polycyclic aromatic hydrocarbon concentrations were quantified in 448 PM2.5 samples and the multiple-site PMF receptor model was based on the elemental and inorganic ion data. Six factors associated with potential sources were quantified, namely, secondary sulfate, ammonium nitrate and combustions, fossil fuels, traffic, industrial and glassmaking. Source apportionment results were further processed using a series of chemometric tools for returning additional information about the seasonal and spatial changes of factors extracted by the PMF analysis. In addition, PMF results were also studied in combination with weather conditions and PAH concentrations revealing that sources of secondary nitrate and sulfate are homogeneously distributed throughout the area, while remaining pollutant sources may have a distinct origin. PMF results were cluster analyzed to sort out samples with similar source profiles and then the wind roses of grouped samples were examined to assess the role of wind speed and direction on PM2.5 pollution and chemistry. The tested tools and the results obtained can be used for air quality assessment studies and air pollution reduction strategies.

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.

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.

The Veneto Region extends for ∼18.4·103 km2 in the northeastern part of the Po Valley and includes mountains, hills, plain and coastal environments with very different and discontinuous anthropogenic pressures. Although many efforts have been made to mitigate air pollution, the European air quality standards for atmospheric pollutants are frequently breached. This study investigates the levels of eight PM10-bound PAHs collected in 21 stations categorized as rural background, urban and suburban backgrounds, traffic and industrial hot-spots during one year (2011). Data were statistically processed to detect the PAH seasonal trends, their relationship with other air pollutants and micro-meteorological parameters and the space variations at a regional scale. Results show that PAHs levels are relatively high in the largest part of the region, with 10 sites exceeding the levels of BaP targeted by the European legislation. Two sites exhibited anomalously high PAHs concentrations and this anomaly became even more evident when considering the population density as a surrogate for the potential anthropogenic pressure. The PAHs levels were found directly proportional to other gaseous pollutants (CO, NO, NOx, SO2) suggesting common polluting sources. The analysis of time trends of PAH concentrations reveals significant coincidences throughout the region, i.e. simultaneous changes are observed in most sites as a consequence of similar emission sources and accumulation/removal processes. In this scenario, the control strategies currently imposed at local level (e.g. traffic limitations) have proven scarcely effective in mitigating air pollution and a real coordination at regional or even interregional level cannot be further postponed. Peculiar features of the PAHs pollution in the Veneto were also identified and some measures for protecting the human health were suggested.

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. Electronic supplementary material The online version of this article (doi:10.1007/s11356-013-2115-x) contains supplementary material, which is available to authorized users.

This study combines a set of chemometric analyses with a source apportionment model for discriminating the weather conditions, local processes and remote contributions having an impact on particulate matter levels and chemical composition. The proposed approach was tested on PM10 data collected in a semi-rural coastal site near Venice (Italy). The PM10 mass, elemental composition and the water soluble inorganic ions were quantified and seven sources were identified and apportioned using the positive matrix factorization: sea spray, aged sea salt, mineral dust, mixed combustions, road traffic, secondary sulfate and secondary nitrate. The influence of weather conditions on PM10 composition and its sources was investigated and the importance of air temperature and relative humidity on secondary components was evaluated. Samples collected in days with similar atmospheric circulation patterns were clustered on the basis of wind speed and direction. Significant differences in PM10 levels and chemical composition pointed out that the production of sea salt is strongly depending on the intensity of local winds. Differently, typical primary pollutants (i.e. from combustion and road traffic) increased during slow wind regimes. External contributions were also investigated by clustering the backward trajectories of air masses. The increase of combustion and traffic-related pollutants was observed when air masses originated from Central and Northwestern Europe and secondary sulfate was observed to rise when air masses had passed over the Po Valley. Conversely, anthropogenic contributions dropped when the origin was in the Mediterranean area and Northern Europe. The chemometric approach adopted can discriminate the role local and external sources play in determining the level and composition of airborne particulate matter and points out the weather circumstances favoring the worst pollution conditions. It may be of significant help in designing local and national air pollution control strategies.

All over Europe, low wind speeds and stable atmospheric stratification are meteorological factors leading to air pollution episodes. Discriminating the contribution of the local atmospheric circulation and the regional and long-range transport processes, in determining PM2.5 and pollutants levels, is very important for deciding any effective abatement measure. This is particularly true in the Northeastern part of the Po Valley, one of the most polluted areas in Europe. This study proposes a method for assessing the relative importance of regional and long-range transport episodes and of local sources on PM2.5 mass and ionic composition. Air mass back-trajectories were combined with PM chemical composition and local wind data and the relative contributions were estimated. Air mass histories show that the levels of PM2.5 increased when air masses had arrived from Northern to Central and Northwestern Europe and significantly dropped when the trajectories originated from the Mediterranean area. Furthermore, results reveal that relatively fast winds from quadrant I were associated with clean air and increasing sea-salt components. Diversely, air mass stagnations were closely accompanied by severe pollution events. Heavily polluted episodes were recorded in correspondence of days characterized by low-mobility atmospheric conditions and when air masses had spent most time over the Po Valley region. These results can help understanding the sources, the chemistry and dynamics of PM2.5 in Northeastern Italy. The proposed approach is easily applicable to other environments.

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, p0.05), as well as that between Intersex development and OTC pollution (n=6, r=0.91, p0.05). 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.

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, 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 Gdańsk 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.

Understanding and controlling air pollution in highly populated areas is very important, although interpreting the levels of gaseous pollutants and airborne particulate matter is complicated by dominant natural and anthropogenic emissions, micro-meteorological processes, and chemical reactions which take place directly in the atmosphere. For this reason, it is very difficult to relate the characteristics of air pollution to one or more specific emission sources. The aim of this paper is to detect associations among elements and organic compounds emitted from specific sources by means of chemical analyses, statistical processing of data, seasonal evolution study, and geochemical considerations to trace their origin. A detailed characterization of air quality during the period September 2000–September 2001 was carried out in three locations of the Venice region: A heavy traffic urban site, a public park, and the island centre of the city of Venice. Twenty-eight inorganic elements, four polycyclic aromatic hydrocarbons, CO and benzene were quantified and processed by a statistical procedure based on factor analysis considering variations on a seasonal basis. Results show the presence of associations between elements and compounds with the same behaviour in all sampling points. This indicates that several pollutants originate from a common source, and are then “diluted” throughout the study area, maintaining the imprint of their origin. Pt, polycyclic aromatic hydrocarbons, CO and benzene originating from the exhaust gas of vehicles are all linked in the traffic factor, whereas Cd is associated with Se, having a common source in industrial processes.

Polychlorobiphenyls, chlorinated pesticides, polycyclic aromatic hydrocarbons and heavy metals (Cd, Pb, Cr, Ni, Hg, Cu, Fe, Zn) were measured in the entire tissue of the mussel Mytilus galloprovincialis, collected at five sites in the Lagoon of Venice and one reference site outside the Lagoon, in the Adriatic Sea. Total concentrations ranged from 57.5 ± 0.2 to 779 ± 11 ng g−1 d.w. for PAHs, from 52 ± 4 to 286 ± 1 ng g−1 d.w. for PCBs, and from 2.6 ± 0.8 to 37 ± 4 ng g−1 d.w. for pesticides, indicating significantly higher contamination in the central part of the Lagoon with respect to the northern and southern ones. As regards heavy metals, only Cd presented a pattern similar to that of organic compounds. The other metals showed peculiar distribution in the six sites of the Lagoon in relation to their sources. The risk to human health as a result of eating these mussels was evaluated by comparison of daily dietary intake with toxicological threshold limits. In mussels from Porto Marghera, Cd, hexachlorobe...

Imposex, namely the superimposition of male characteristics, such as penis and vas deferens, on females of gonochoristic gastropods is one of the most harmful effects of TBT on marine organisms. The development of such malformations on marine organisms have led to limitations in the use of TBT in antifouling paints in several countries. Regulation 782/2003 by the EU prohibits the application of organotin compounds. However, in other non EU Mediterranean countries, such as Croatia, the IMO convention has failed to be transposed into domestic legislation and TBT-based antifouling paints are still used. Different restrictions to TBT use and, consequently, likely different levels of TBT contamination between Italy and Croatia gave the cue to this work, whose aims are: (a) monitoring organotin compound levels and imposex degree in Hexaplex trunculus, a common gastropod in the Mediterranean Sea, and an exhibitor of imposex; (b) assessing the level of organotin compounds build-up in the visceral coil and in the rest of the soft body (ROSB) of this organism, in order to try to understand how H. trunculus metabolizes these pollutants; (c) investigating the relationship between organotin compound concentrations in tissues of H. trunculus and the level of imposex development. The results indicate that the incidence of imposex is still high in Italy (Lagoon of Venice) after more than 10 years from the ban of TBT-based antifouling paints. The sampling in Croatian coasts indicates that the absence of restrictions on the use of TBT is likely to cause very high levels of OTC contamination.

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.

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 g mol−1) to hexachlorobenzene (MW=284.78 g mol−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.

With the objective of improving qualitative characteristics of compost, an analytical survey was carried out in a composting plant in Lombardy (Italy) in all process of production, with particular reference to heavy metals (HM) Zn and Pb. The investigation was principally aimed to study the contents and the accumulation of HM during composting process and to identify a technological solution for reducing HM content in the final product. A merceological analysis of Municipal Solid Waste (MSW) input to the composting plant, a chemical analysis of the organic fraction of MSW after mechanical separation, and a comparison with values reported by some authors, showed that Zn and Pb are significant contaminants, even though concentrations have recently decreased in comparison to previous years. On the basis of Zn and Pb content in raw material input to the plant, an estimate of the theoretical value of Zn and Pb in produced compost was made. The comparison of theoretical values with the real ones, experimentally determined, confirmed that at the end of composting process the concentration is 2.6 times the initial value for Zn and 1.6 times the initial value for Pb, as suggested by some authors. Finally, the analytical investigation of Zn and Pb contents in the compost refining line, carried out by means of sieving tests, showed that by eliminating a fraction of compost < 1 mm, both Zn and Pb, which is the more critical one, can be largely removed, without a substantial yield loss (only 10% of the final product is eliminated).

Toxicol.andEnviron.Chem., Vol. 84, No. 1–4, pp. 53–67 2001 OPA (Overseas Publishers Association) N.V.Reprints available directly from the publisher Published by license underPhotocopying permitted by license only the Gordon and Breach SciencePublishers imprint,a member of the Taylor & Francis Group.

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.

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.

A simulation model was built to describe the growth patterns of Zostera marina in an area in the Venice lagoon. The model tracks changes in the above- and below-ground biomass and shoot density and is based on data for Zostera biomass, net production and growth rates, chemical-physical parameters and nutrient concentrations in water, sediment and particulate matter. It was assumed that the most important factors controlling Zostera growth and distribution are light and temperature, and that Zostera growth was not limited by nutrient availability. The goal was to simulate biomass production and its seasonal changes as a function of external forcing variables (light, water temperature, wind and tide-generated water movements) and internal control (plant density). A series of simulation experiments were performed with the basic model and its modifications showed that among the most important phenomena affecting Zostera growth are: (1) inhibition of production and recruitment of new shoots by high temperature and (2) light attenuation due to seasonal fluctuation and wind- and tide-induced suspension of sediments.

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.

The amending characteristics and effectiveness as fertiliser of a compost obtained from park and yard trimmings, sludge and food residuals (mostly from municipal solid wastes), have been tested. Differences in fertility and other parameters occurring among compost amended soil, soil treated with chemical nutrients and untreated soil were tested. The compost progressively provided the soil with organic matter and assimilable nutrients, while not increasing soil salinity. Concentrations of some heavy metals, however increased in the compost treated soil, suggesting the need for long‐term monitoring of soils treated with composts.

A simple method for a simultaneous gas chromatographic determination of polyclorobiphenyls and polycyclic aromatic hydrocarbons in samples of sewage sludge and compost is described. Certified materials were used for the evaluation of the method. Organic micropollutants were extracted from freeze-dried samples through a mixture of organic solvents - n-hexane/dichloromethane, 4:1 v:v-in a sonification bath. A multilayer clean-up/ separation column was used to remove interfering organic compounds and to divide PCBs and PAHs into two distinct fractions; and additional purification with metallic mercury was necessary to eliminate sulphur. Fractions are quantifiable with GC-ECD and GC-MS-SIM. The method was applied to determine the concentrations of both PCBs and PAHs during the composting process; a characteristic time profile was traced.

In this study, the Active BioMonitoring (ABM) approach has been investigated using species of indigenous (from a pristine site) and transplanted (to a polluted area) hard clam Mercenaria mercenaria as an indicator organism of water/sediment pollution in Tampa Bay, Florida, a highly urbanized and industrialized subtropical estuary. A range of possible induced stress indices was selected and used on the basis of potential pollutant toxicity mechanisms including specific enzymatic responses (MFO as BPH and NADPH cytochrome c reductase, antioxidant enzymes as SOD and caltalase, PDH) and general cellular damage (lysosomal latency, histopathological lesions). The organic sediment contamination compared to the animal body burden revealed bioaccumulation activity in transplanted clams. The marked increases of BPH and catalase activities, together with the significant reduction of lysosomal membrane stability in transplanted animals, suggested their potential for application as biomarkers in subtropical coastal pollution monitoring.

Recent research trends in sediment quality assessment have demonstrated the need for an integrated approach which combines chemical characterisation with biological effects evaluation, both in the laboratory (toxicity bioassays) and in situ (macrobenthic community structure investigations). The Sediment Quality Triad organises these three aspects of sediment quality assessment in a single approach, where each component is complementary to the others. Considering the lack of previous studies, this preliminary work aimed to verify the potential of an integrated approach in a complex ecosystem, the Venetian lagoon. Five sampling stations along a presumed quality gradient were chosen. The chemical analyses of heavy metals and organic pollutants have been compared with the results of the toxicity bioassays (Microtox® solid phase, saline extracts and pore water, and sea urchin Paracentrotus lividus sperm cell bioassay performed with saline extracts) and with the characterisation of the infaunal community structure. The results of this first application pointed out the complementarity of the three approaches and the ability of the integrated approach in discriminating different levels of environmental stress. Nevertheless, deeper investigations both on the response of the macrobenthic community to natural variability and on the environmental toxicity of several sulphur compounds (i.e. elemental sulphur) will be necessary.

Chemical analyses and bioassays were used in conjunction to assess the quality of sediments of the Venice lagoon. Organic micropollutants (polycyclic aromatic hydrocarbons [PAHs] polychlorinated biphenyls [PCBs], and chlorinated pesticides) were extracted from sediment samples and analyzed by gas chromatography after fractionation into classes of compounds. The Vibrio fischeri test was used to assess the acute toxicity of sediment extracts. The test was applied to organic extracts before cleanup and to extracts purified from sulfur and fractionated into single classes of compounds. Extracts before purification were much more toxic than single fractions. In particular, sulfur was toxic to V. fischeri. For PAHs and PCBs the 50% effective concentration (EC50) and EC20 values were determined using natural and spiked extracts (EC50 = 0.5 μg/ml and 1.4 μg/ml, respectively; EC20 = 0.13 μg/ml and 0.17 μg/ml). Sensitivity limits of the method for these compounds were also estimated as was an EC50 value of elemental sulfur dissolved in ethanol (0.022 μg/ml). A mathematical model was used to fit the concentration–response data to a sigmoid curve.

Estuaries and coastal zones are dynamic transitional systems which provide many economic and ecological benefits to humans, but also are an ideal habitat for other organisms as well. These areas are becoming contaminated by various anthropogenic activities due to a quick economic growth and urbanization. This chapter explores the sources, chemical speciation, sediment accumulation and removal mechanisms of the harmful elements in estuarine and coastal seawaters. It also describes the effects of toxic elements on aquatic flora and fauna. Finally, the toxic element pollution of the Venice Lagoon, a transitional water body located in the northeastern part of Italy, is discussed as a case study, by presenting the procedures adopted to measure the extent of the pollution, the impacts on organisms and the restoration activities.

Vibrio fisheri test has been used to evaluate the toxicity of contaminated sediment of the Venice lagoon. The following classes of organic microcontaminants were considered in this study: aliphatic hydrocarbons (AHs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and chlorinated pesticides. Contaminants were extracted from samples with n‐hexane/dichloromethane in a sonication bath. Extracts were then purified and fractionated with column chromatography. A solvent exchange into ethanol was made before testing, to reduce toxicity. Preliminary tests were performed to set up the procedure to apply Vibrio fisheri to organic extracts. The application of the test with organic extracts was made at different steps of clean‐up and fractionation into classes of compounds. The purpose of the study was to set up a procedure to comparatively assess sediment contamination with chemical analyses and toxicity bioassays.

The space-time distribution of some pollutants (Cu, Pb, Zn, Cd, Fe, Mn, V, Ni, Cr) in the sludge of the canals of Venice was studied. The contamination levels were comparable to, or higher, than those measured in the most polluted sediments of the Lagoon of Venice. Sediments were collected by two different sampling techniques: 1) collection of sediment cores (upper 5 cm) by a syringe-type corer; 2) collection by traps, placed on the bottom of the canal. Traps permitted the sampling of sediments essentially resuspended by overlying water turbulence. This sediment fraction is subjected to variations of its physicochemical parameters (principally change of redox conditions) and therefore to pollutant exchange at the water/sediment interface.

This study presents a part of a project aiming at characterizing the PM10 composition in the Venice area with detailed chemical analyses using various techniques. The concentrations of six major inorganic ions (Cl−, NO3−, SO42−, Na+, NH4+, Mg2+) and 19 elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Pb) were quantified using ion chromatography and PIXE, respectively. The masses of PM10 daily samples and their chemical contents were studied in relationship to micro-meteorological parameters to select a few of them characterized by very different chemical profiles. Four samples from the whole period were categorized as representative of i) clean days; ii) sea spray generation events; iii) high contribution of mineral dust and iv) heavy pollution events. Individual particle analyses of the samples were also performed by SEM-EDS microscopy. Six different classes of particles were identified (mineral particles, chlorides, sulfates, elemental and organic carbon compounds, metals an...

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.

A multiannual multipurpose experiment on atmospheric properties is being carried on at the Svalbard Islands, starting in year 2010. Major reasons of interest, both climatic and chemical, concerning the study of atmospheric aerosol, together with basic experimental features will be presented. Detailed results being presented concern 40 size-segregated aerosol samples collected in year 2010 (4 days sampling time) with a 12-stage SDI impactor and PIXE analyzed. Elemental Mass Size Distributions are fitted with lognormal functions. Up to three size modes (super-and sub-micrometric; intermediate) are determined for each element. Emphasis is given to the crustal aerosol component, due its crucial climatic role. Position, width and intensity of each mode of element Si are displayed, together with the ratios of the concentration of Al, Fe, Ti Mn (and possibly other elements) vs. Si, in the supermicrometric mode. These data will be used for singling out the major crustal components and helping determining their origin and their interaction with radiation.