Debora Fabbri

Anticancer drugs are considered pseudo-persistent pollutants for the water environmental compartments due to their continuous emission into water bodies. Many sources contribute to the bioaccumulation of the drugs, and the investigation of their residues and transformation products (TPs) fate is mandatory, in particular for compounds displaying a high degree of toxicity. Here, we present a High-Performance Liquid Chromatography – High-Resolution Mass Spectrometry (HPLC-HRMS) method developed to identify and characterize the TPs of cyclophosphamide (CYC), 5-fluorouracil (5FU) and oxaliplatin (OXA), subjected to heterogenous photocatalysis mediated by titanium dioxide. The irradiation experiments were performed at different times, and the HPLC separation was achieved using a reverse-phase column. A high-resolution Orbitrap mass analyzer was used in the positive and negative ionization modes with a resolution of 30k. Tandem mass spectrometry experiments were acquired in the CID activation mode. With the developed method, we recognized and tentatively assigned the structures of six TPs for CYC, four TPs for 5FU and one TPs for OXA. The developed analytical method was then applied to real environmental water samples coming from nine sampling sites of Po River (Italy). We found the presence of CYC in four site points at level of ppb. The developed HPLC-HRMS method was a satisfactory tool to identify anticancer drugs and their TPs and to quantify them in real water environmental samples.

The chemical composition of the soluble fraction of atmospheric particulate matter (PM) and how these components can combine with each other to form different species affect the chemistry of the aqueous phase dispersed in the atmosphere: raindrops, clouds, fog, and ice particles. The study was focused on the analysis of the soluble fraction of Arctic PM₁₀ samples collected at Ny-Ålesund (Svalbard Islands, Norwegian Arctic) during the year 2012. The concentration values of Na⁺, K⁺, NH₄⁺, Ca²⁺, Mg²⁺, Mn²⁺, Cu²⁺, Zn²⁺, Fe³⁺, Al³⁺, Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, PO₄³⁻, formate, acetate, malonate, and oxalate in the water-soluble fraction of PM₁₀ were determined by atomic spectroscopy and ion chromatography. Speciation models were applied to define the major species that would occur in aqueous solution as a function of pH (2–10). The model highlights that (i) the main cations such as Na⁺, K⁺, Mg²⁺, and Ca²⁺ occur in the form of aquoions in the whole investigated pH range; (ii) Cu²⁺, Zn²⁺, and, in particular, Fe³⁺ and Al³⁺ are mostly present in their hydrolytic forms; and (iii) Al³⁺, Fe³⁺, and Cu²⁺ form solid hydrolytic species that precipitate at pH values slightly higher than neutrality. These latter metals show interesting interactions with oxalate and sulfate ions, too. The speciation models were also calculated considering the seasonal variability of the concentration of the components and at higher concentration levels than those found in water PM extracts, to better simulate concentrations actually found in the atmospheric aqueous phase. The results highlight the role of oxalate as the main organic ligand in solution. Graphical Abstract

Biodegradable, waste-derived hydrogels containing immobilised peroxidase were successfully used for enzymatic removal of organic pollutants in water. Hydrogels are reusable and provide detoxification of the contaminants solution.

This study investigated the direct and indirect photochemical degradation of citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), under natural and artificial solar radiation. Experiments were conducted in a variety of different operating conditions including Milli-Q (MQ) water and natural waters (lake water and municipal WWT effluent), as well as in the presence of natural water constituents (organic matter, nitrate and bicarbonate). Results showed that indirect photolysis can be an important degradation process in the aquatic environment since citalopram photo-transformation in the natural waters was accelerated in comparison to MQ water both under natural and simulated solar irradiation. In addition, to investigate the decontamination of water from citalopram, TiO₂-mediated photocatalytic degradation was carried out and the attention was given to mineralization and toxicity evaluation together with the identification of by-products. The photocatalytic process gave rise to the formation of transformation products, and 11 of them were identified by HPLC-HRMS, whereas the complete mineralization was almost achieved after 5 h of irradiation. The assessment of toxicity of the treated solutions was performed by Microtox bioassay (Vibrio fischeri) and in silico tests showing that citalopram photo-transformation involved the formation of harmful compounds.

Soil is a non-renewable natural resource. However, the current rates of soil usage and degradation have led to a loss of soil for agriculture, habitats, biodiversity, and to ecosystems problems. Urban and former industrial areas suffer particularly of these problems, and compensation measures to restore environmental quality include the renaturation of dismissed areas, de-sealing of surfaces, or the building of green infrastructures. In this framework, the development of methodologies for the creation of soils designed to mimic natural soil and suitable for vegetation growth, known as constructed soils or technosols, are here reviewed. The possible design choices and the starting materials have been described, using a circular economy approach, i.e., preferring non-contaminated wastes to non-renewable resources. Technosols appear to be a good solution to the problems of land degradation and urban green if using recycled wastes or by-products, as they can be an alternative to the remediation of contaminated sites and to importing fertile agricultural soil. Nevertheless, waste use requires analysis to ensure the salubrity of the starting materials. Moreover, materials produced on site or nearby minimize the cost and the environmental impact of transport, thus the involvement of local stakeholders in the urban land management must be encouraged.

Rationale: Bisphenol E (BPE) and bisphenol S (BPS) have recently replaced bisphenol A as monomers for producing polycarbonates. However, BPE and BPS can pose hazards as they are known to be endocrine disruptors. Despite the huge increase in their use, there is a lack of data regarding the toxicity and effects of BPE and BPS. Methods: We investigated the photoinduced transformation of BPE and BPS when subjected to sun‐simulated radiation and using TiO ₂ as a photocatalyst. Analyses of BPE, BPS and their by‐products were performed by high‐performance liquid chromatography/high‐resolution mass spectrometry (HPLC/HRMS) using an orbitrap mass analyzer in negative electrospray ionisation (ESI) mode. The chromatographic separations were achieved by employing a C18 reversed‐phase column, and the transformation products (TPs) were elucidated structurally using HRMS and multistage MS experiments performed in collision‐induced dissociation (CID) mode. Results: The transformation of bisphenol S involved the formation of twelve by‐products, while ten TPs were detected following BPE degradation. For bisphenol S, the cleavage of the molecule is a very important transformation route, together with the hydroxylation of the substrate to provide mono‐ and poly‐hydroxylated TPs. For bisphenol E, the two main routes were hydroxylation and ring opening. Acute toxicity for BPS, BPE and their TPs was assessed using the Vibrio fischeri assay, highlighting that their initial transformation involved the formation of TPs that were more toxic than the parent compound. Conclusions: The HPLC/HRMS method developed was useful for characterising and identifying newly formed TPs from bisphenol E and bisphenol S. This study aimed to examine the structure of twenty by‐products identified during TiO ₂ ‐mediated photolysis and to evaluate acute toxicity over time.