Plastic debris incidence in marine environment was already highlighted in the early 1970s. Over the last decade, microplastic pollution in the environment has received increasing attention and is now an emerging research area. Many studies have focused on quantifying microplastic abundance in the marine environment, while there are relatively few data on microplastic occurrence in freshwater environment. Recent studies have reported high concentrations of microplastics in lakes and rivers, although the understanding of several factors influencing source, transport and fate is still limited. This study compares different lakes and the common factors, which could influence the occurrence and distribution of microplastics. The three subalpine lakes monitored include Lake Maggiore, Iseo and Garda. The selected sampling transects reflect the hydrologic conditions, the morphometric characteristics of these lakes, and other factors influencing the release of plastics debris in lakes. Particles of microplastics (<5 mm) were found in all sampled surfaces. The particles collected were classified depending on their number, shape and composition. The shape distribution showed the dominating occurrence of fragments (73.7%). The chemical composition of all examined samples clearly shows dominating presence of polyethylene (45%), polystyrene (18%) and polypropylene (15%). The results provide significant relations among the different contribution of direct and diffuse sources to the quantity of microplastics, highlighting the importance of understanding the spatial distribution dynamics of microplastics within a lake system that acts as a sink and source of plastic particles.

Lake tributaries collect contaminants from the watershed, which may accumulate in lake sediments over time and may be removed through the outlets. DDx, PCB, PAH, PBDE, and trace element (Hg, As, Cd, Ni, Cu, Pb) contamination was analyzed over 2001–2018 period in sediments of the 5 main tributaries and of the outlet of Lake Maggiore (Northern Italy). Sediment cores were collected in two points of the lake, covering 1995–2017 period. Concentrations were compared to Sediment Quality Guidelines (PECs), potential sources and drivers (land use, population numbers, industrial activities, hydrology) were analyzed, and temporal trends were calculated (Mann-Kendall test). PCB, PBDE, Pb, Cd, and Hg contamination derives mainly from heavy urbanization and industry. Cu and Pb show a temporal decreasing trend in the basin, likely as result of improved wastewater treatments and change in use. A recent PAH increase in the whole lake may derive from a single point source. A legacy DDx and Hg industrial pollution is still present, due to high persistence in sediments. Values of DDx, Hg, Pb, and Cu above the PECs in lake sediments and/or in the outlet show potential risk for aquatic organisms. Results highlight the key role of tributaries in driving contamination from the watershed to the lake through sediment transport.

In 1996, dichlorodiphenyltrichloroethane (DDT) pollution of industrial origin was discovered in Lake Maggiore. It was caused by industrial effluents on a tributary of the River Toce, one of the major affluents of the lake in correspondence of Pallanza Bay. This event is the worst case of environmental pollution that has occurred in Western countries in the last 25 years, not due to agricultural use of DDT, but because of an accidental industrial discharge. Heavy polychlorinated biphenyls (PCBs) pollution was also noticed in 2002, with concentration levels three to seven times higher than those measured in other Italian subalpine lakes. In this study, the current DDT and PCBs contamination levels were assessed according to their presence in zebra mussel (Dreissena polymorpha) specimens sampled in the last 5 years (2003-2008) in eight sampling stations of Lake Maggiore, chosen to cover the entire perimeter of the basin. Moreover, for two stations (Baveno and Pallanza-Villa Taranto) located inside and outside Pallanza Bay, respectively, it is possible to make comparisons starting from 1996. The results obtained show how Lake Maggiore is still an ecosystem with a severe environmental risk, more than 10 years after the original insecticide discharge. DDT contamination continues to evolve, and natural events, like lake overturn, floods, and heavy rains, can have a great influence on the insecticide levels in the lake. By contrast, PCB contamination is absolutely negligible, even if the peak of pollution revealed in 2002 seems to indicate that these pollutants are still present in large quantities in the Lake Maggiore watershed.

A growing concern exists about the effects of chloride (Cl) on freshwater systems. Increasing Cl concentrations have been observed in the last few decades in several rivers and lakes, mainly in northern countries. In Italy, present levels and temporal changes of sodium (Na) and Cl in water bodies have rarely been assessed. Based on long-term data for the lakes of the subalpine district in Italy (Maggiore, Lugano, Como, Iseo, Garda), we analyzed trends affecting Cl and Na concentrations during the last 25 years, with the aim of identifying temporal changes and assessing possible causes. An in-depth analysis is presented for Lake Maggiore. Positive temporal Na and Cl trends were evident in all studied lakes, with the trends increasing since early 2000s. Data for Lake Maggiore tributaries showed a clear seasonality (higher values in winter and early spring). The NaCl used as road de-icing agent, together with Cl discharge from wastewater treatment plants, were identified as the main causes for the observed trends. Chloride concentrations in the lakes are below the threshold limit for reduced water quality and below concentrations known to harm aquatic biota. However, considering the relevance of deep subalpine lakes, representing almost 80 % of the total freshwater volume in Italy, these trends indicate an important chemical change, which warrants further analysis.

Background In the present study, we report the analytical results of pp′DDT, pp′DDE and pp′DDD determination in lake water, plankton and zooplanktivorous fish of Lake Maggiore (Northern Italy), rather recently polluted by DDT of industrial origin, in order to understand the bottom-up pollution transfer among the abiotic and biotic components of the lake ecosystem. Materials and methods Fourteen water sampling campaigns were carried out from March 2003 to January 2009 in the water column of the deepest point (Ghiffa) of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Three sampling campaigns were carried out from July 2008 to January 2009 for zooplankton and pelagic fish, and DDT residues were analysed by HRGC coupled with ECD and MS. Moreover, food items were detected in fish stomachs. Results and discussion Starting from 2007, the DDT contamination along the water column became rather homogeneous, probably because no flooding or other relevant hydrological events occurred; although steady-state condition should be expected, lipid normalised concentrations of pp′DDE and pp′DDD in zooplankton exceeded the levels of the same compounds in zooplanktivorous fishes. Conclusion As this finding represents a thermodynamic paradox since bioaccumulative pollutant concentrations are expected to increase along the trophic chain, it was supposed that the abiotic and biotic lake components were not in a steady-state condition in Lake Maggiore.

The Lake Maggiore (Northern Italy) has been recognized as an aquatic environment heavily contaminated by persistent organic pollutants, mainly organochlorine compounds, but to date limited information is available regarding another class of widespread and hazardous pollutants, such as the polycyclic aromatic hydrocarbons (PAHs). The aim of this study was to investigate seasonal and temporal trends of 18 PAHs accumulated in native Dreissena polymorpha specimens during a 5-year biomonitoring program, as well as to identify the possible PAH emission sources by using isomeric diagnostic ratios. Zebra mussels were sampled both in their pre- (May) and post-reproductive (September) stage over the 2008–2012 period in eight sampling stations covering the whole lake shoreline. PAH concentrations were measured through gas chromatography coupled to mass spectrometry. A notable PAH contamination following an increasing temporal trend was noticed in bivalves from all the sampling stations, with the benzo(α)anthracene as the predominant compound. An overall increase in PAH levels was found in the post-reproductive surveys, indicating a marked seasonality of this contamination probably due to the increase in touristic activity during spring–summer months.

Because of the reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), started to be marketed as alternatives to the banned formulations. In this study, the spatial distribution and accumulation of NBFRs, PBDEs, and HBCD in the biota have been investigated in the littoral compartment of a large and deep subalpine lake (Lake Maggiore, Northern Italy), using zebra mussel Dreissena polymorpha and roach (Rutilus rutilus) as bioindicators. To our knowledge, this is the first study reporting the contamination of NBFRs in the freshwater invertebrate D. polymorpha. Contamination of zebra mussel due to PBEB, HBB, and BTBPE was low, ranging from 0.9 to 2.9 ng/g lipid weight, from 1.1 to 2.9 ng/g l.w., and from 3.5 to 9.5 ng/g l.w., respectively. PBEB and BTBPE in roach were always below the detection limit, while the contamination of HBB ranged from < limits of detection (LOD) to 1.74 ng/g l.w., indicating a weak contamination. DBDPE was < LOD in all the considered biological samples. Finally, HBCD was detected in all organic tissues with mean concentrations up to 74.4 ng/g l.w. PBDE results, supported by principal component analysis elaboration, suggested a possible contamination due to the congeners composing the penta- and deca-BDE technical formulations, which are present in the Lake Maggiore basin. The biomagnification factor values showed that tetra- and penta-BDE biomagnified, while octa-, nona-, and deca-BDE were still bioavailable and detectable in the fish muscles, but they do not biomagnified. Considering the other BFRs, only HBCD showed a moderate biomagnification potential.

DDT and mercury (Hg) contamination in the Toce River (Northern Italy) was caused by a factory producing technical DDT and using a mercury-cell chlor-alkali plant. In this study, DDT and Hg contamination and bioavailability were assessed by using different approaches: (1) direct evaluation of sediment contamination, (2) assessment of bioaccumulation in native benthic invertebrates belonging to different taxonomic/functional groups, and (3) evaluation of the in situ bioavailability of DDT and Hg using passive samplers. Sampling sites were selected upstream and downstream the industrial plant along the river axis. Benthic invertebrates (Gammaridae, Heptageniidae, and Diptera) and sediments were collected in three seasons and analyzed for DDT and Hg content and the results were used to calculate the biota sediment accumulation factor (BSAF). Polyethylene passive samplers (PEs) for DDT and diffusive gradients in thin films (DGTs) for Hg were deployed in sediments to estimate the concentration of the toxicants in pore water. Analysis for (DDx) were performed using GC-MS. Accuracy was within ±30 % of the certified values and precision was >20 % relative standard deviation (RSD). Total mercury concentrations were determined using an automated Hg mercury analyzer. Precision was >5 % and accuracy was within ±10 % of certified values. The results of all the approaches (analysis of sediment, biota, and passive samplers) showed an increasing contamination from upstream to downstream sites. BSAF values revealed the bioavailability of both contaminants in the study sites, with values up to 49 for DDx and up to 3.1 for Hg. No correlation was found between values in sediments and the organisms. Concentrations calculated using passive samplers were correlated with values in benthic invertebrates, while no correlation was found with concentrations in sediments. Thus, direct analysis of toxicant in sediments does not provide a measurement of bioavailability. On the contrary, analysis of bioaccumulation in benthic organisms provides the most realistic picture of the site-specific bioavailability of DDx and Hg, but this approach is time-consuming and not always feasible. On the other hand, the in situ deployment of passive samplers proved to be a powerful tool, providing a good surrogate measure of bioaccumulation.

Since the 1990s, the Lake Maggiore (Northern Italy) has been recognized as an aquatic environment contaminated by DDTs and other persistent organic pollutants, but to date just few studies were carried out to investigate the effects of pollution to aquatic organisms. The aim of this study was the application of a stepwise approach based on chemical data, a suite of biomarkers and the integration of their responses into a biomarker response index (BRI) to evaluate the site-specific quality assessment in different sampling stations of Lake Maggiore, one of the largest European lakes. We used as biological model the freshwater bivalve Zebra mussel (Dreissena polymorpha). Several hundred bivalve specimens were sampled on May 2011 from eight sampling sites located along the lake shoreline. We measured levels of DDTs, PCBs, HCHs, HCB, and PAHs accumulated in D. polymorpha soft tissues by GC/MSn, while the activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione S-transferase, as well as the lipid peroxidation and protein carbonyl content were evaluated in homogenates from native bivalves as oxidative stress indices. Moreover, DNA damage was investigated by the alkaline precipitation assay. Significant imbalances of enzymatic activity were found in mussels from most of the sampling sites, as well as notable increases of damage to macromolecules. Health status of mussels from Baveno was greatly affected by lake pollution, probably due to high levels of DDTs measured in this site, while a wide variability in biomarker responses was found in all the other stations. The application of a BRI allowed distinguishing impacts of pollution to bivalves, confirming mussels from Baveno as the most threatened and revealing that also the health status of bivalves from Suna, Brissago, Pallanza, and Laveno is affected. These evidences suggest the usefulness of a specific index to integrate all the biomarker endpoints in order to provide a correct environmental risk assessment.