Contaminants of emerging concern in water and sediment of the Venice Lagoon, Italy.

This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three hormones, six pharmaceutical compounds (diclofenac and five antibiotics, three of which are macrolides), nine pesticides (methiocarb, oxadiazon, metaflumizone, triallate, and five neonicotinoids), one antioxidant (BHT), and one UV filter (EHMC). Water and sediment samples were collected in seven sites in four seasons, with the aim of investigating the occurrence, distribution, and possible emission sources of the selected CECs in the studied transitional environment. The most frequently detected contaminants in water were neonicotinoid insecticides (with a frequency of quantification of single contaminants ranging from 73% to 92%), and EHMC (detected in the 77% of samples), followed by BHT (42%), diclofenac (39%), and clarithromycin (35%). In sediment the highest quantification frequencies were those of BHT (54%), estrogens (ranging from 35% to 65%), and azithromycin (46%). Although this baseline study does not highlight seasonal or spatial trends, results suggested that two of the major emission sources of CECs in the Venice Lagoon could be tributary rivers from its drainage basin and treated wastewater, due to the limited removal rates of some CECs in WWTPs. These preliminary results call for further investigations to better map priority emission sources and improve the understanding of CECs environmental behavior, with the final aim of drawing up a site-specific Watch List of CECs for the Venice Lagoon and support the design of more comprehensive monitoring plans in the future.

Nanosized titanium dioxide particle emission potential from a commercial indoor air purifier photocatalytic surface: A case study.

Background: Photocatalytic air purifiers based on nano-titanium dioxide (TiO 2) visible light activation provide an efficient solution for removing and degrading contaminants in air. The potential detachment of TiO 2 particles from the air purifier to indoor air could cause a safety concern. A TiO 2 release potential was measured for one commercially available photocatalytic air purifier "Gearbox Wivactive" to ensure a successful implementation of the photocatalytic air purifying technology. Methods: In this study, the TiO 2 release was studied under laboratory-simulated conditions from a  Gearbox Wivactive consisting of ceramic honeycombs coated with photocatalytic nitrogen doped TiO 2 particles. The TiO 2 particle release factor was measured in scalable units according to the photoactive surface area and volume flow (TiO 2-ng/m 2×m 3). The impact of  Gearbox Wivactive on indoor concentration level under reasonable worst-case conditions was predicted by using the release factor and a well-mixed indoor aerosol model. Results: The instrumentation and experimental setup was not sufficiently sensitive to quantify the emissions from the photoactive surfaces. The upper limit for TiO 2 mass release was <185×10 -3 TiO 2-ng/m 2×m 3. Under realistic conditions the TiO 2 concentration level in a 20 m 3 room ventilated at rate of 0.5 1/h and containing two Gearbox Wivactive units resulted <20×10 -3 TiO 2-ng/m 3. Conclusions: The release potential was quantified for a photocatalytic surface in generalized units that can be used to calculate the emission potential for different photocatalytic surfaces used in various operational conditions. This study shows that the TiO 2 nanoparticle release potential was low in this case and the release does not cause relevant exposure as compared to proposed occupational exposure limit values for nanosized TiO 2. The TiO 2 release risk was adequately controlled under reasonable worst-case operational conditions.

Assessing glyphosate in water, marine particulate matter, and sediments in the Lagoon of Venice.

Lagoon water, suspended particulate matter, and sediment samples from seven sites at Lagoon of Venice were collected from 2019 to 2021 in order to study the presence of the herbicide glyphosate (N-(phosphonomethyl)glycine), among the most widely used agricultural chemicals worldwide, but its occurrence in lagoon water environment has not been deeply investigated. The sites were selected considering a supposed diversity of inputs and of pollution levels. An analytical method based on ion chromatography coupled with tandem mass spectrometry was optimized and validated for lagoon water, marine particulate matter, and sediment samples. Maximum concentrations of glyphosate were 260 and 7 ng L-1 for lagoon water and suspended particulate matter, respectively, and 15 ng g-1 for sediment, with some spatial and temporal fluctuations. Our results demonstrate that glyphosate content in the Venice Lagoon mainly depends on external forcing from river inlets and agricultural lagoon activities.

Small microplastics (<100 µm), plasticizers and additives in seawater and sediments: Oleo-extraction, purification, quantification, and polymer characterization using Micro-FTIR.

In this study, the abundance and the distribution of small microplastics (<100 µm, SMPs) and of other components of micro-litter (i.e., additives, plasticizers, natural and non-plastic synthetic fibers, APFs) were investigated in sediments and seawater of three different sites of a transitional environment; different anthropogenic impacts and environmental features characterize these three sites. The pretreatment method developed (oleo-extraction and purification procedures) allowed the collection of particles (SMPs and APFs) in a wide range of densities, e.g., from low-density plastics to high-density plastics, avoiding further degradation/denaturation of polymers. An analytical method for quantification and simultaneous identification of SMPs and APFs via Micro-FTIR was developed. Higher abundances of SMPs were observed in sediments compared to the abundance observed in seawater. SMPs were not the major component of the micro-litter. With natural fibers and non-plastic fibers, additives and plasticizers were quantified and identified in sediments and seawater. These latter are employed to obtain specific characteristics of polymers; hence their presence can be a good proxy of these polymers' presence in the environment. Sources and pathways may influence the abundance and distribution of SMPs and APFs. Differences in abundance and distribution of these pollutants in sediments and seawater of the three sites investigated were statistically significant.

Occurrence and source apportionment of organic pollutants in deep sediment cores of the Venice Lagoon.

In this study, recent and aged inputs of five classes of organic contaminants (i.e. PCBs, OCPs, PCDD/Fs, PAHs, and n-Alkanes) were evaluated in eight deep sediment cores of the Venice Lagoon, collected along the path of a new waterway whose excavation is under evaluation by local authorities, to assess the environmental quality status of the area. Diagnostic indices were calculated for identifying pollutant distribution patterns and their major emission sources, whose relative contribution was quantified by a Positive Matrix Factorization source apportionment model. Sedimentary depth profiles highlighted higher contamination in the top layer, mainly related to ship traffic combustion and vehicular/industrial emissions from the mainland. Nevertheless, a significant level of pollution has been detected also in the deeper layers, probably due to the transport of particulate matter through the aquifers underlying the lagoon seabed. The results underlined the threat posed by the possible resuspension of pollutants in the water column during contaminated sediment dredging.

Geospeciation, toxicological evaluation, and hazard assessment of trace elements in superficial and deep sediments.

To evaluate the hazard assessment of dredging and disposal of sediments, an in-depth chemical and toxicological characterization of sediments was carried out in Venice Lagoon. The bioaccessible and mobile concentration of trace elements in superficial and deep sediments (in the Holocene-Pleistocene limit) can deeply affect the quality of the aquatic ecosystem. Geospeciation and total concentration of trace elements in sediment cores were assessed and several toxicological tests were carried out. The indices of contamination (e.g., geochemical accumulation index, Igeo, pollution load index, PLI) and of speciation (individual contamination factor, ICF and global contamination factor, GCF) were evaluated. Factor Analysis (FA) was performed to explore possible significant correlations between toxicity data and sediment chemistry. Results underlined that the total concentration of trace elements cannot adequately assess the hazard, while bioavailability, mobility, and toxicity of trace elements allow a thorough evaluation of the environmental threats. The integration of results from chemical characterization ex ante and toxicity assays will provide for a better sustainable handling and management of sediments.

Interannual variability of sugars in Arctic aerosol: Biomass burning and biogenic inputs.

The concentrations and particle-size distribution of sugars in Arctic aerosol samples were studied to investigate their potential sources and transport. Sugars are constituents of the water-soluble organic compounds (WSOC) fraction in aerosol particles where some saccharides are used as tracers of Primary Biological Aerosol Particles (PBAPs). Monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), disaccharides (sucrose, lactose, maltose, lactulose), alcohol-sugars (erythritol, mannitol, ribitol, sorbitol, xylitol, maltitol, galactitol) and anhydrosugars (levoglucosan, mannosan and galactosan) were quantified in aerosol samples collected during three different sampling campaigns (spring and summer 2013, spring 2014 and 2015). The mean total concentrations of sugars were 0.4 ± 0.3, 0.6 ± 0.5 and 0.5 ± 0.6 ng m-3 for 2013, 2014 and 2015 spring campaigns, while the mean concentration increased to 3 ± 3 ng m-3 in the summer of 2013. This work identified a reproducibility in the sugars trend during spring, while the summer data in 2013 allowed to us to demonstrate strong local inputs when the ground was free of snow and ice. Furthermore, the study aims to show that the two specific ratios of sorbitol & galactiol to arabinose were diagnostic for the type of biomass that was burnt. This study demonstrates that not only is long-range atmospheric transport significant. But depending on seasonality, local inputs can also play an important role in the chemical composition of sugars in Arctic aerosol.

Dissolved organic matter in the deep TALDICE ice core: A nano-UPLC-nano-ESI-HRMS method.

Trace organic compounds in deep ice cores supply important paleoclimatic information. Untargeted analyses of dissolved organic matter provide an overview of molecular species in ice samples however, sample volumes usually required for these analyses are generally not available from deep ice cores. Here, we developed an analytical method using a nano-UPLC-nano-ESI-HRMS to detect major molecular species in ice cores. Samples (4 µL) from the TALos Dome Ice CorE (TALDICE), allowed investigating molecular species across a range of depths including during glacial and interglacial periods. We detected 317 chemical species that were tentatively assigned to fatty acids, hydroxy fatty acids and their degradation products (oxo-fatty acids and dicarboxylic acids), as well as oxidation byproducts of isoprene and monoterpenes. These compounds indicate that the main sources of the organic fraction are microbes as well as primary and secondary aerosols. Interglacial samples encompass a wide range of species including compounds from the oxidation of isoprene and monoterpenes as well as unsaturated fatty acids, while the glacial samples contained less diverse species. This difference may be due to decreased temperatures during the glacial period inhibiting terrestrial vegetation growth and increasing the sea ice extent, thereby weakening the emission sources.

Temporal evolution of cadmium, copper and lead concentration in the Venice Lagoon water in relation with the speciation and dissolved/particulate partition.

In order to study the role of sediment re-suspension and deposition versus the role of organic complexation, we investigated the speciation of cadmium (Cd), copper (Cu) and lead (Pb) in samples collected in the Venice Lagoon during several campaigns from 1992 to 2006. The increment in Cd and Pb concentration in the dissolved phases, observed in the central and northern basins, can be linked to important alterations inside the lagoon caused by industrial and urban factors. The study focuses on metal partition between dissolved and particulate phases. The analyses carried out in different sites illustrate the complex role of organic matter in the sedimentation process. While Cd concentration in sediments can be correlated with organic matter, no such correlation can be established in the case of Pb, whose particulate concentration is related only to the dissolved concentration. In the case of Cu, the role of organic complexation remains unclear.

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. Graphical abstract Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter and evaluation of the effect of an European Directive on air quality in Venice.