Fate and effects of a new generation fluorosurfactant (cC6O4) in freshwater mesocosms.

Per- and polyfluorinated alkyl substances (PFAS) have raised international concerns due to their widespread use, environmental persistence and potential bioaccumulative and ecotoxicological effects. Therefore, the chemical industry has been dedicated to develop new generation fluorosurfactants which are aimed to replace the most concerning PFAS. Here we investigated the fate and effects of cyclic C6O4 (cC6O4), a compound used as alternative to long-chain perfluorocarboxylic acids, in freshwater mesocosms located in the Mediterranean region (Spain) over a period of 90 days. cC6O4 was applied as ammonium salt once at the following nominal concentrations: 0 µg/L (control), 1 µg/L, 20 µg/L, 400 µg/L, and 8,000 µg/L. The study shows that cC6O4 is relatively persistent in water (dissipation: 34-37 % after 90 days), has very low sorption capacity to sediments (sediment-water partition coefficient: 0.18-0.32 L/kg) and very limited bioconcentration (BCF: 0.09-0.94), bioaccumulation (BAF: 0.09-4.06) and biomagnification (BMF: 0.05-0.28) potential. cC6O4 did not result in significant adverse effects on aquatic populations and communities of phytoplankton and zooplankton at the tested concentrations. As for the macroinvertebrate community, the ephemeropteran Cloeon sp. showed a population decline at the highest test concentration on day 60 onwards, and a significant effect on the macroinvertebrate community was identified on the last sampling day at the same exposure level. Therefore, the calculated NOEC for cC6O4 in freshwater mesocosms exposed over a period of 90 days was 400 µg/L, which corresponded to a time weighted average concentration of 611 µg/L, given the water evaporation in the test systems. This concentration is about an order of magnitude higher than the highest exposure concentration monitored in freshwater ecosystems. Therefore, it can be concluded that cC6O4 poses insignificant ecological risks for freshwater plankton and macroinvertebrate communities given the current environmental exposure levels.

Toxicity and bioaccumulation of the fluorosurfactant cC6O4 in the earthworm Eisenia foetida (Savigny, 1826).

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether PFAS used as a polymerization aid in the synthesis of fluoropolymers and produced in Italy since 2011 as substitute of PFOA. To date, available ecotoxicological information on cC6O4 is related to regulatory requirements and limited to data on aquatic organisms, while the information on the effects for terrestrial organisms is completely lacking. This work reports the first ecotoxicological data of cC6O4 on terrestrial invertebrates: short- and long-term toxicity of cC6O4 on Eisenia foetida (Savigny, 1826), exposed to spiked soil under laboratory conditions, was investigated evaluating the earthworm survival and growth (observed after 7, 14 and 28 days of exposure), and reproduction (observed after an exposure period of 56 days). Furthermore, also bioaccumulation was investigated (28 days of exposure); overall results are discussed in comparison with literature data available for legacy PFAS. cC6O4 did not cause significant mortality on earthworms, for any of the tested concentrations and exposure periods (NOEC: > 1390 mg/kg d.w.), while the reproduction (measured as juveniles production) appears to be a more sensitive endpoint (EC50: 10.4 mg/kg d.w., EC10: 0.8 mg/kg d.w.). The observed adverse effects occur at levels significantly higher than realistic soil concentrations and cC6O4 appears to be less toxic than PFOA and PFOS. As for bioaccumulation, the results indicate a negligible bioaccumulation potential of cC6O4, whose Biota-Soil Bioaccumulation Factors (BSAF) are significantly lower than all other considered PFAS.

Uptake of cyclic C6O4 in maize and tomato: Results from a greenhouse study.

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether used as a polymerization aid in the synthesis of fluoropolymers and produced since 2011 as substitute of PFOA. This work reports the first data on bioaccumulation of cC6O4 on terrestrial plants (maize and tomato). In general, the observed accumulation and translocation of cC6O4 in plants is low or negligible. For maize a bioconcentration factor (BCFdw/dw) of about 39 was observed in the root compartment and much lower (BCFdw/dw = 12) in the aboveground tissues. In tomato the observed BCFs are substantially lower, with a maximum of 2.5 in leaves. The differences observed between the uptake and distribution of cC6O4 in maize and tomato plants are probably due to differences in plant physiology (but also in the experimental design of the tests). Maize plants grown at different concentrations in this study did not show relevant differences in term of biomass and growth, while tomato plants exposed to cC6O4 were subject to a delay in the ripening of the fruits (and relative biomass). The overall results are discussed in comparison with literature data available for legacy PFASs but the comparison is difficult due to differences in the experimental design. It is relevant to note that the concentrations tested in this study are significantly higher than expected environmental concentrations.

Environmental exposure and ecotoxicological properties of a new-generation fluorosurfactant (cC6 O4 ): A comparison with selected legacy perfluoroalkyl acids.

Cyclic C6 O4 (cC6 O4 , CAS number 1190931-27-1) is a new-generation polyfluorinated alkyl substance (PFAS) used as a polymerization aid in the synthesis of fluoropolymers, which has been produced in Italy since 2011. A review of the properties of cC6 O4 , focused on environmental distribution and ecotoxicology, was conducted. The EQuilibrium Criterion model was applied, using default environmental scenarios, to estimate environmental distribution and fate. In a situation of static thermodynamic equilibrium in a closed system (Level I), cC6 O4 distributes mainly to water (97.6%) and in a minimal amount to soil (2.3%). In a more realistic scenario (Level III), with dynamic conditions in an open system, with advection in air and water and with equal emissions in air and water, the major amount of the compound is transported through water advection. Monitoring data, mainly referring to surface and groundwater, are available for water bodies close to the production sites (maximum measured concentration 52 µg/L) as well as for a wider area in the river Po watershed with concentrations generally lower than 1 µg/L. Few values are also available for concentration in biota. Effect data indicate low toxicity on all tested organisms with no observed effect concentration (NOEC) values always higher than the maximum concentrations tested (100 mg/L for acute tests). Bioaccumulation potential is also very low. A comparison with selected widely used PFAS with five to eight C atoms indicates that cC6 O4 is substantially less dangerous to aquatic organisms. For the time being, an ecological risk for the aquatic ecosystem may be excluded even in directly exposed ecosystems. However, for a complete assessment of the suitability of cC6 O4 as a substitute for other PFAS (namely, perfluorooctanoic acid), more comprehensive chronic experiments are necessary, to produce realistic NOEC, as well as higher tier experiments (e.g., mesocosms) capable of providing ecologically relevant endpoints. Moreover, a more accurate evaluation of the environmental persistence would be necessary. Integr Environ Assess Manag 2023;19:1636-1648. © 2023 SETAC.

Ecological risk assessment for contaminated sites in Italy: Guidelines and path forward.

Ecological risk assessment (ERA) is defined as an iterative process that evaluates the likelihood of adverse ecological effects resulting from exposure to one or more stressors. Although ERA is recognized as a valuable procedure to better address efforts and strategies for site remediation, in Europe a common framework for the implementation of ERA in the management of contaminated sites is lacking. In Italy, there are no legally binding provisions regulating the direct assessment of potential likelihood of ecological risks. In this context, the main objective of this article was to develop a guideline to facilitate ERA application in support of an effective and sustainable management of contaminated sites in Italy and to facilitate a multistakeholder dialogue. The work was based on a critical review of existing ERA guidelines in the international context, as well as other regulatory documents and technical approaches dealing with the evaluation of ecological effects of chemical contaminants in different environmental compartments. Approaches and tools available in these documents were then used to prepare a proposed guideline for the Italian context; the proposed ERA guideline is meant to represent a flexible but robust approach that can be useful in evaluating existing data (e.g., from past investigations) as well as in the planning of site-specific investigations. To facilitate the direct application of the ERA procedure, the guideline was prepared including several templates of summary tables, checklists, and examples. The proposed ERA guideline could facilitate the decision-making process for contaminated sites with ecological values, although its application would necessarily require, at least in the initial phase, testing of its suitability to the Italian context and setting-up of a close dialogue and collaboration with local authorities and other stakeholders. Integr Environ Assess Manag 2023;19:913-919. © 2022 SETAC.

Pre-industrial sediment concentrations of metals: insights from the Venice lagoon (Italy).

This study investigated the occurrence of selected metals and metalloids (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) in radio-dated sediment cores from a coastal lagoon (Lagoon of Venice, Italy) by critically reviewing and grouping available data. Pre-industrial concentrations (pICs, estimated for the period before the early 1900s) for the Venice lagoon are identified according to the 2σ statistical procedure (2σ-pICs), i.e., the upper bound values of the dataset distribution. Results show the following 2σ-pICs (µg/g, d.w.): As 15,9; Cd 0,6; Cr 38,0; Cu 18,1; Hg 1,1; Ni 32,9; Pb 29,4; Zn 94,5. Most of the estimated 2σ-pICs are comparable to previously assessed background values. In the case of Hg, on the contrary, 2σ-pIC is remarkably higher than background values, reflecting a significant anthropogenic contribution also in the pre-industrial period. The results of this work may support the evaluation of the temporal evolution of metal concentrations in sediments of the Venice lagoon. Results are compared with background concentrations (BC) observed in previous studies conducted in the lagoon and in other areas of the Adriatic Sea, as well as with benchmarks set in Italy for sediment assessment.

Persistent organic pollutant in a fish community of a sub-alpine lake.

This study investigated the presence of organochlorine pollutants in abiotic and biotic samples from Lake Como (Italy). DDTs and PCBs were found to be the major contaminants, ranging from 0.04 to 4.25 and from 0.25 to 40.8 µg/g lipid respectively. Evidence of biomagnification according to the trophic role of the investigated organisms was highlighted by means of Stable Isotope Analysis. A Trophic Magnification Factor (TMF) was calculated for the chemicals of interest and the applicability of the method for global use was confirmed. Statistically significant correlation has been found between the calculated trophic level and the concentrations of more lipophilic compounds, while for the less lipophilic (e.g., HCH, 3CBs) the relationship is no statistically significant and the TMF is close to 1. The role of the foraging area in affecting PCB and DDT concentrations within aquatic ecosystems has been highlighted by a Principal Component Analysis (PCA).