Antonio Tagarelli

A rapid and environmentally sustainable analytical method was developed for the simultaneous determination of nitrophenols, nitroguaiacols, and nitrocatechols in environmental water samples. The proposed strategy integrates aqueous-phase derivatization with ethyl chloroformate, dispersive pipette extraction (DPX), and gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) into a streamlined workflow that minimizes organic solvent consumption, sample handling, and total analysis time. Derivatization was performed directly in the aqueous matrix under mild conditions, enabling seamless coupling with the DPX procedure. Multivariate experimental design was applied to optimize both derivatization parameters and programmed temperature vaporization (PTV) injection conditions, efficiently identifying the most influential factors while minimizing the number of experiments required. Under optimized conditions, the method provided extraction recoveries of 55–82%, excellent linearity (R2 ≥ 0.9986), and limits of quantification ranging from 0.3 to 5 µg/L. Accuracy ranged between 84 and 119% with relative standard deviations below 17.5%, while matrix effects were negligible for the investigated water matrices. Notably, the proposed method enables, for the first time, the simultaneous determination of nitrophenols, including dinitrophenols, nitroguaiacols, and nitrocatechols in environmental water samples, significantly expanding the analytical scope beyond previously reported approaches. Greenness was evaluated using the AGREEprep metric, confirming the low environmental impact of the protocol. The developed method represents a powerful, reliable, and analytically comprehensive tool for the large-scale monitoring of nitroaromatic phenols in environmental waters.

The recovery of lithium from extracts obtained from a black mass of spent lithium-ion batteries treated with a ternary solvent system at acidic pH was investigated using flat-sheet nanofiltration (NF) membranes operated according to a dead-end configuration. Specifically, four samples obtained at different pH values (2.5 and 5) and extraction times (48, 96 and 168 h) were treated in selected operating conditions by using two commercial polymeric membranes (denoted DK and HL, with an approximate molecular weight cut-off of 150–300 Da) up to a volume reduction factor (VRF) of 4. Membrane performance was assessed in terms of productivity and selectivity towards specific ions, including lithium. For most treated samples, the HL membrane exhibited higher permeate fluxes in comparison to the DK membrane. However, the DK membrane performed better in terms of lithium rejection than the HL membrane, with a negative rejection at VRF 4 observed for all treated samples. More than 90% of multivalent ions were rejected by both membranes independently of the VRF. The membrane ability to retain multivalent ions led to their progressive concentration in the retentate as the VRF increased. The extraction time did not impact the NF performance of both membranes in terms of ion rejection. For the DK membrane conditions of extraction of 96 h and pH 5 represented the best trade-off between flux, ion rejection, and total lithium recovery.

In this review, a 5-year overview on environmentally friendly approaches for the extraction of the most relevant organic pollutants in soil, sediment, particulate matter, and sewage sludge coupled with chromatographic analysis is reported. Organic contaminants encompass various compounds derived from personal care products, industrial chemicals, microplastics, organic matter combustion, agricultural practices, and plasticizer material. The principles of green analytical chemistry (GAC) and green sample preparation (GSP) serve as a guideline for the development of more environmentally sustainable analytical protocols. This study focuses attention on microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE), matrix solid-phase dispersion (MSPD), and microextraction techniques, such as solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), hollow-fiber liquid-phase microextraction (HF-LPME), spray-assisted droplet formation-based liquid-phase microextraction (SADF-LPME), and dispersive liquid–liquid extraction (DLLME). These approaches represent the most relevant eco-friendly sample preparation for the advanced extraction of target analytes from environmental solid samples.

The increasing use of agrochemicals, including fertilizers and herbicides, has led to worrying metal contamination of soils and waters and raises serious questions about the effects of their transfer to different levels of the trophic web. Accumulation and biomagnification of essential (K, Na, Mg, Zn, Ca), nonessential (Sr, Hg, Rb, Ba, Se, Cd, Cr, Pb, As), and rare earth elements (REEs) were investigated in newly emerged adults of Tenebrio molitor exposed to field-admitted concentrations of a metribuzin-based herbicide and an NPK blend fertilizer. Chemical analyses were performed using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) supported by unsupervised pattern recognition techniques. Physiological parameters such as cuticle melanization, cellular (circulating hemocytes), and humoral (phenoloxidase enzyme activity) immune responses and mass loss were tested as exposure markers in both sexes. The results showed that NPK fertilizer application is the main cause of REE accumulation in beetles over time, besides toxic elements (Sr, Hg, Cr, Rb, Ba, Ni, Al, V, U) also present in the herbicide-treated beetles. The biomagnification of Cu and Zn suggested a high potential for food web transfer in agroecosystems. Gender differences in element concentrations suggested that males and females differ in element uptake and excretion. Differences in phenotypic traits show that exposure affects metabolic pathways involving sequestration and detoxification during the transition phase from immature-to-mature beetles, triggering a redistribution of resources between sexual maturation and immune responses. Our findings highlight the importance of setting limits for metals and REEs in herbicides and fertilizers to avoid adverse effects on species that provide ecosystem services and contribute to soil health in agroecosystems.

Lead (Pb), due to its high toxicity and bioaccumulation tendency, is one of the top three pollutants of concern for both humans and wildlife and occupies second place in the Priority List of Hazardous Substances. In freshwater fish, Pb is mainly absorbed through the gills, where the greatest accumulation occurs. Despite the crucial role of gills in several physiological functions such as gas exchange, water balance, and osmoregulation, no studies evaluated the effects of environmentally relevant concentrations of Pb on this organ, and existing literature only refers to high levels of exposure. Herein we investigated for the first time the molecular and morphological effects induced by two low and environmentally relevant concentrations of Pb (2.5 and 5 μg/L) on the gills of Danio rerio, a model species with a high translational value for human toxicity. It was demonstrated that Pb administration at even low doses induces osmoregulatory dysfunctions by affecting Na⁺/K⁺-ATPase and AQP3 expression. It was also shown that Pb upregulates MTs as a protective response to prevent cell damage. Modulation of SOD confirms that the production of reactive oxygen species is an important toxicity mechanism of Pb. Histological and morphometric analysis revealed conspicuous pathological changes, both dose- and time-dependent.