Multi-Year Concentrations, Health Risk, and Source Identification, of Air Toxics in the Venice Lagoon

This work presents and discusses the results of multi-year measurements of air toxics concentrations from different sites of Venice Lagoon. The aim of the study is the characterization of the air quality of the area, in terms of PM10, PM10-bound metals, and polycyclic aromatic hydrocarbons (PAHs) concentrations, even with the individuation of the related inhalation risk and the identification of the main contaminants' sources. The study moreover provides an important multi-years trend of chemical characterization of the Venice Lagoon. Sampling for PM10 and its metal content was carried out between 2010 and 2015, using low volume sequential aerosol samplers; V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb were measured by ICP-MS. Samples for PAHs concentration in gas and particle phases were collected from 2010 to 2014, using a high-volume air sampler that allows to sample both phases simultaneously. Samples for PAHs determinations were analyzed by GC-HRMS. Concentrations of air toxics have been studied with the use of enrichment factor, the coefficient of divergence, and the Mann-Kendal test, to individuate eventual local divergences, seasonal and other temporal trends. The inhalation risk assessment has been achieved by the calculation of the cumulative incremental carcinogenic risk for all the air toxics analyzed. The sources' identification and impact evaluation have been carried out using the atmospheric vanadium concentration, to calculate the primary contribution of ship traffic to PM10, the Positive Matrix Factorization, and the Diagnostic Ratios, with the aim of evaluating the impact of construction activities of M.o.S.E, (Modulo Sperimentale Elettromeccanico-Electromechanical Experimental Module) as well as of ship traffic and other possible air toxics' sources. Temporal trends indicate a slight decrease of PAHs and PM10 and of its content of Pb, Zn, Sb. Sharp increases of As and Cd during 2014 and 2015 may be due to local sources like emissions from the construction yard, ship, and road traffic. The cumulative incremental carcinogenic risk was below the unconditionally acceptable risk; Co and As are the most important contributors among metals, followed by Cd and Ni while the PAH congeners that most contribute to the carcinogenic risk were benzo(a)pyrene and dibenzo(A,H)anthracene

Shipping and Air Quality in Italian Port Cities: State-of-the-Art Analysis of Available Results of Estimated Impacts

Populated coastal areas are exposed to emissions from harbour-related activities (ship traffic, loading/unloading, and internal vehicular traffic), posing public health issues and environmental pressures on climate. Due to the strategic geographical position of Italy and the high number of ports along coastlines, an increasing concern about maritime emissions from Italian harbours has been made explicit in the EU and IMO (International Maritime Organization, London, UK) agenda, also supporting the inclusion in a potential Mediterranean emission control area (MedECA). This work reviews the main available outcomes concerning shipping (and harbours') contributions to local air quality, particularly in terms of concentration of particulate matter (PM) and gaseous pollutants (mainly nitrogen and sulphur oxides), in the main Italian hubs. Maritime emissions from literature and disaggregated emission inventories are discussed. Furthermore, estimated impacts to air quality, obtained with dispersion and receptor modeling approaches, which are the most commonly applied methodologies, are discussed. Results show a certain variability that suggests the necessity of harmonization among methods and input data in order to compare results. The analysis gives a picture of the effects of this pollution source, which could be useful for implementing effective mitigation strategies at a national level

Fragrances as new contaminants in the Venice lagoon

FragranceMaterials (FMs) are omnipresent components of household and Personal Care Products (PCPs). In spite of their widespread use, little is known about their environmental occurrence. We selected 17 among the longest-lasting and most stable fragrance ingredients that are commercially available, namely: Amberketal, Ambrofix, Amyl Salicylate, Benzyl Salicylate, Bourgeonal, Dupical, Hexyl Salicylate, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Oranger Crystals, Pelargene, Peonile, Tridecene-2-Nitrile, Ultravanil. A new analytical method was developed to quantify FMs in water samples and it was applied to perform the first study about the distribution of these compounds in the surface waters of the city of Venice and its lagoon. Total FMs concentrations range from about 30 ng L-1 to more than 10 mu g L-1 in polluted canals during the low tide. Sewage discharges were supposed to be the main sources of the selected FMs in the environment. Salicylates, oestrogenic and allergenic compounds, were in general the most abundant and widespread components. This study reports for the first time the detection of most of the selected FMs in surface waters and represent the first step to understand their environmental fate. (C) 2016 Elsevier B.V. All rights reserved

Antioxidant properties and chemical composition relationship of Europeans and Brazilians propolis

The antioxidant activity of ethanol extracts of propolis, bee glue, of various climate and orographic characteristics, col- lected from Italy, Brazil and Russia, was evaluated measuring their inhibitory action on peroxidation of linoleic acid, radical scavenging ability towards 2,2’-diphenyl-1-picrylhydrazyl, total phenolic content and reducing capacity by en- zymatic and Folin method respectively. Propolis samples were chemically characterized by HPLC-MS/MS in order to find a possible correlation between antioxidant activity and polyphenols composition and quantification. The results obtained indicate that Italian and Russian propolis samples have similar polyphenolic composition and, as a consequence, almost similar antioxidant activity, while Brazilian propolis evidence lower polyphenolic and antioxidant characteristics. Climate and orography reasons of these differences are also suggested

Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter in Venice air

Harbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals

Evaluation of the toxicological impact of textile industry using a multi-criteria ranking of toxic compounds

Conducting a global toxicological evaluation of chemicals is a considerable challenge, as each single chemical is characterised by specific toxicological features (lethal effects, carcinogenicity, etc.). Given the increasing concern regarding the use of chemicals in everyday life and workplaces, in recent years several methods for chemical hazard screening have been developed [1, 2]. In all cases, a limited number of categories was defined, thus significant difference in toxicity among chemicals could be minimised. In this work, a number of chemicalswere subjected to a toxicological ranking based on the most important types of toxicity using multi-criteria analysis (MCA). Data about pollutant global hazard and concentration values in wastewater were combined to provide an indication about the toxicological impact of textile factories. GreenPeace identified eleven classes of hazardous chemicals that should be eliminated by top brands in the framework of the "Detox" campaign [3], with the aim of reducing water pollution caused by the textile industry. The MCA ranking included the above mentioned classes of chemicals with the addition of cyanide, given its known lethal effect. The types of toxicity selected as criteria were: acute toxicity, carcinogenicity, reproductive toxicity, acute aquatic toxicity and chronic aquatic toxicity, in this order of importance. Heavy metals and cyanide were the most dangerous compoundsidentified by the assessment. On average, the most polluting facilities were located in India and China. Since incoming water was usually characterised by a minimum toxicological impact, the responsibility for the high toxicity scores of facilities wereassigned to the suppliers

Tyre Wear Particles and Small Microplastics (SMPs <100 Μm) From Highway Stormwater Runoff: Sampling, Pre-Treatment Procedures and First Results

Highway stormwater runoff is a direct pathway for conveying microplastics (MPs) and other environmental pollutants from land-based sources to the aquatic and terrestrial environment. However, the concerns on stormwater for microplastic pollution and the other components of microlitter (additives and plasticizers) have grown exponentially and the knowledge on their pathways and impacts are now very limited. Important sources of microplastic in stormwater runoff are related to traffic vehicles, polymer-modified bitumen, road paint, atmospheric deposition and the wear of tyres. Hence, due to their small size, smaller MPs (SMPs, &lt; 100 μm), additives and tyre wear particles (TWPs) can pose a risk for the environments as they can be ingested by different kinds of biota and can cause potential health problems for human beings. Only very limited studies have been paid attention to microplastics, especially SMPs, and TWPs from highway stormwater runoff with a consequent lack of knowledge regarding the amounts, size, and composition of these pollutants emitted in the different environmental pathways. There are currently no standardized methods and harmonized techniques for the collection, pretreatments, contamination procedures, and analysis of SMPs and TWPs from stormwater runoff, making significant differences in the data of these pollutants studies difficult to compare. In this study, stormwater runoff samples were collected during different rainfall events from a trafficked highway near Venice, Italy. A pre-treatment procedure (e.g., oleo-extraction, purification, and filtration) was developed and optimized in a Clean Room (ISO 7) at Ca’ Foscari University of Venice to prevent any possible plastic contamination. Quantification and simultaneous chemical identification were performed via MicroFTIR for SMPs, TWPs, additives, and plasticizers in stormwater runoff samples. Further, pyrolysis gas chromatography-mass spectrometry (Pyr-GC/MS) was developed to confirm the presence of specific SMPs and TWPs in the same samples analyzed. The cross-validation among MicroFTIR and Pyr-GC/MS techniques allows the standardization of pretreatment and analytical methods. Regarding TWPs, different tests were carried out and the first results of quantification and chemical identification of specific markers were obtained

POPs paleoenvironmental record over the last 220 years from an ice core retrieved at the plateau site of Dome C, Antarctica

Persistent organic pollutants (POPs) are ubiquitous in the environment and are affected by long-range atmospheric transport (LRAT) due to their low vapour pressure. Therefore, these substances have been found in almost every environmental matrix worldwide, including the remote regions of Arctic and Antarctica [1-4]. Polar environments are almost free of local sources and are an ideal site for studying global contamination. Analyzing pollutants in ice cores can reveal the history of atmospheric transport and deposition, and can be useful for studying the variation of the sources over the years and the contribution of human activities to global pollution. In this work we obtained the POPs depth profile of a 16.5 m deep ice core (covering 212 years before present) drilled at the plateau site of Dome C, East Antarctica (75°06' South Latitude, 123°21' East Longitude), during the 23rd Italian Antarctic Expedition. Specifically, we analyzed 25 sections of the core investigating the presence of six classes of organic pollutants: polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzo-p-furans (PCDFs) and polybrominated diphenyl ethers (PBDEs). The core covers a time interval which includes periods before and after the introduction of these POPs in commercial mixtures, as well as periods before the construction of research station facilities. Thus, the analysis of this core assumes considerable importance in assessing the impact of these choices to POPs global contamination. A recent paper investigated the presence of PCBs and PAHs in an ice core gathered at peripheral site GV7, Talos Dome, along the East Antarctic coast [3]. However, as to our knowledge this is the first study focusing on the simultaneous analysis of so many classes of POPs in an ice core, and this is the first analysis of organic pollutants in a core from the Antarctic plateau, which is the most remote area in the world. The pre-analytical procedures were adapted, reducing the required target liquid volume per sample to 500 mL, in order to obtain a profile with a higher temporal resolution respect to what have been previously reported [2-3]. To minimize contamination, all the procedures were carried out in a clean laboratory equipped with laminar flow hoods (class from 10.000 to 1.000). Ice samples were analyzed by Gas Chromatography coupled both to Low-Resolution, High-Resolution and Tandem Mass Spectrometry (LRMS, HRMS, MS/MS). [1] Dickhut et al., 2012. Environ. Sci. Technol. 46, 3135-3140. DOI: 10.1021/es204375p [2] Garmash et al., 2013. Environ. Sci. Technol. 47, 12064-12072. DOI: 10.1021/es402430t [3] Giannarelli et al., 2017. Chemosphere 174, 390-398. DOI: 10.1016/j.chemosphere.2017.01.126 [4] Polkowska et al., 2011. Sensors 11, 8910-8929. DOI: 10.3390/s11090891

Microplastics in the freshwater and earthbound conditions: prevalence, destinies, impacts and supportable arrangements

An increasing number of researches have been published on MPs’ different freshwater ecosystems worldwide, including lakes, rivers, estuaries, and wetlands in both waters and sediments. Although the literature on plastics in freshwater is growing, data are globally disjointed about the evidence of concentrations of MPs and impacts on environmental freshwater matrices [1]. Besides, the heterogeneity of sampling protocols, methodologies, techniques, and measurement units among different researches makes it challenging to compare results and produce a complete picture of the existing state of understanding [2]. Another critical factor is that MPs&lt;100 μm (SMPs) are often overlooked; less than 20% of reported studies on freshwater environments reported MPs below 20 μm. The sampling and analytical procedures are strictly connected to detecting plastic particles sizes &gt;100 μm. Consequently, most of the reported studies could have undervalued the concentration of SMPs. Thus, improvement in detection technologies and pre-treatments methods could modify the final mean amount of MPs in freshwater environments [3]. Freshwater systems are considered an important source and critical pathway for MP pollution in coastal and marine environments, especially for the point sources close to areas with a high density of population and civilization [4–6]. Research in freshwater environments has detected MPs in Europe, North America, Africa, Asia, and Antarctica. The USA has performed the most research on MPs of all freshwater microplastics studies, followed by China [7]. Regarding water, the most polluted areas are Southeast Asia and Europe, while sediments are also highly contaminated in North Africa and North America [1]. Thus, MPs are widespread pollutants not only in marine systems but also in freshwater systems. Studies on MPs in freshwater systems are mainly conducted in rivers, lakes, and estuaries, while new research has focused on wetlands, stormwater ponds, and reservoirs. However, there is limited knowledge about MPs in these freshwater environments compared to rivers and lakes [2, 8]

Microplastics analysis: can we carry out a polymeric characterisation of atmospheric aerosol using direct inlet Py-GC/MS?

Microplastics are emerging pollutants of great concern since they are widely distributed in the environment. While the occurrence of microplastics was studied in marine and freshwaters, sediments, soil, and different classes of organisms, the atmosphere was somewhat understudied, although it can be the most significant transport pathway from mid to high latitudes. This work is one of the first studies testing the possible application of pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) for detecting polymers in atmospheric aerosol. It explored the possibility of a direct inlet analysis of sampling filters, proposing for the first time the calculation of an "aerosol organic baseline" for estimating the level of interferences to specific polymer tracers due to the organic matter content of atmospheric aerosol. The direct inlet analysis was tested for environmental samples and commercial dust, using the micro-FTIR analytical technique as a reference. Polyethylene (PE), polypropylene (PP), and polystyrene were detected in atmospheric aerosol samples; PE, PP, and Nylon 6 (polyamide 6, PA6) were detected in the commercial dust. The first results obtained on the atmospheric aerosol allow for highlighting the technique's potential and drawing insights from the difficulties encountered. Results suggest that the direct analysis of the sampling filters can be employed as an exploratory technique due to its fast response, even if further research is needed to obtain a comprehensive polymeric characterisation of atmospheric aerosol