HPLC-MS/MS multiclass determination of steroid hormones in environmental waters after preconcentration on the carbonaceous sorbent HA-C@silica

In this study, a sensitive and multiclass method has been developed for analysis of three families of steroid hormones, i.e. progestins, oestrogens, androgens, by SPE-HPLC-ESI-MS/MS. The extraction efficiency of thermally condensed humic acids onto silica sorbent (HA-C@silica), here for the first time studied for multiclass enrichment of these sex hormones, was tested in different environmental waters (tap and river water, urban wastewater treatment plant effluent) spiked at the nanograms per litre levels (5–1000 ng L−1). Quantitative adsorption was achieved using 200 mg sorbent for preconcentration of 250–1000 mL sample, at the native pH (pH = 6.5–7.7). Elution was performed by two sequential fractions (methanol followed by acetonitrile), obtaining in all the matrices investigated satisfactory recoveries (71% to 124% for river waters and 71–113% for urban wastewater treatment plant effluent) and RSDs below 15% (n = 3). The high enrichment factors (up to 4000) coupled with high-performance liquid chromatography tandem mass spectrometry quantification (MRM mode) provided low limits of detection and quantification (a few ng L−1), that are suitable for environmental monitoring. Most of the analytes were detected in river water and in wastewater effluent samples (in the ng L−1 concentration range), attesting their environmental diffusion. The proposed method was extended to a fourth class, Glucocorticoids, achieving good results in river samples, by the same SPE cartridge and chromatographic run. Keywords: Environmental waters, Steroid hormones, Multiclass determination, HPLC-MS, Pollutants, Solid-phase extractio

Combined Layer-by-Layer/Hydrothermal Synthesis of Fe3O4@MIL-100(Fe) for Ofloxacin Adsorption from Environmental Waters

: A simple not solvent and time consuming Fe3O4@MIL-100(Fe), synthesized in the presence of a small amount of magnetite (Fe3O4) nanoparticles (27.3 wt%), is here presented and discussed. Layer-by-layer alone (20 shell), and combined layer-by-layer (5 shell)/reflux or /hydrothermal synthetic procedures were compared. The last approach (Fe3O4@MIL-100_H sample) is suitable (i) to obtain rounded-shaped nanoparticles (200-400 nm diameter) of magnetite core and MIL-100(Fe) shell; (ii) to reduce the solvent and time consumption (the layer-by-layer procedure is applied only 5 times); (iii) to give the highest MIL-100(Fe) amount in the composite (72.7 vs. 18.5 wt% in the layer-by-layer alone); (iv) to obtain a high surface area of 3546 m2 g-1. The MIL-100(Fe) sample was also synthesized and both materials were tested for the absorption of Ofloxacin antibiotic (OFL). Langmuir model well describes OFL adsorption on Fe3O4@MIL-100_H, indicating an even higher adsorption capacity (218 ± 7 mg g-1) with respect to MIL-100 (123 ± 5 mg g-1). Chemisorption regulates the kinetic process on both the composite materials. Fe3O4@MIL-100_H performance was then verified for OFL removal at µg per liter in tap and river waters, and compared with MIL-100. Its relevant and higher adsorption efficiency and the magnetic behavior make it an excellent candidate for environmental depollution

Solitary Fibrous Tumours of the Pleura

Solitary fibrous tumours of the pleura (SFTP) are rare neoplasms originating from one of the components of the sub-mesothelial connective layer underlying the pleura. They are the most common non-mesothelial primary pleural neoplasms but still remain relatively rare. Their behaviour is mostly indolent; however, some may de-differentiate into malignant and aggressive tumours. Surgical resection is the mainstay treatment for SFTP, even more so in case of voluminous masses, due to compression onto lung, mediastinum and great vessels. In this chapter, we discuss the disease characteristics reported in the literature with respect to clinical presentation, diagnosis and treatment; also, we will discuss the results of patients treated for SFTP who underwent a surgical treatment in our unit of thoracic surgery

Enhancement of TiO2 NPs Activity by Fe3O4 Nano-Seeds for Removal of Organic Pollutants in Water

The enhancement of the photocatalytic activity of TiO2 nanoparticles (NPs), synthesized in the presence of a very small amount of magnetite (Fe3O4) nanoparticles, is here presented and discussed. From X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses, the crystallinity of TiO2 nanoparticles (NPs) seems to be affected by Fe3O4, acting as nano-seeds to improve the tetragonal TiO2 anatase structure with respect to the amorphous one. Photocatalytic activity data, i.e., the degradation of methylene blue and the Ofloxacin fluoroquinolone emerging pollutant, give evidence that the increased crystalline structure of the NPs, even if correlated to a reduced surface to mass ratio (with respect to commercial TiO2 NPs), enhances the performance of this type of catalyst. The achievement of a relatively well-defined crystal structure at low temperatures (Tmax = 150 \u25e6C), preventing the sintering of the TiO2 NPs and, thus, preserving the high density of active sites, seems to be the keystone to understand the obtained results

Evidence of Low-Habitat Contamination Using Feathers of Three Heron Species as a Biomonitor of Inorganic Elemental Pollution

The concentration of 12 elements (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) has been investigated in the feathers of three species of Ardeidae, namely the Grey Heron Ardea cinerea, the Little Egret Egretta garzetta, and the Cattle Egret Bubulcus ibis, all breeding at a colony located in the southern Padana Plain (NW Italy). This study is a first step for an evaluation of possible direct effects of these elements on chicks’ survival and growth rate. Fe, Zn, Cu, and Mn were in the range 7–69 mg Kg−1, while lower levels of Pb, Ni, As, and Se (0.27–1.45 mg Kg−1) were measured. Co, Cd, and Cr were close to the method detection limits (MDLs) in all the species. The measured concentrations of the most abundant trace elements, such as Zn and Cu, seem to reflect the geochemical pattern of the background (running water and soil), while Hg concentration is lower and it appears to be biomagnified, particularly in Grey Heron feathers. Its concentration is higher in adults than in chicks, and it differs among the three species, as it is closely related to the fish-based dietary pattern. The measured trace elements’ concentrations are below the threshold levels in all the heron species, and consequently, harmful and acute effects on the local population are unlikely; the conservation status of herons populations in northern Italy is probably more affected by other factors, such as climate changes, altered aquatic environment, and, consequently, food quality

Fluoroquinolone antibiotics in environmental waters: sample preparation and determination

The aim of this review is to provide a general overview on the analytical methods proposed in the last decade for trace fluoroquinolone (FQ) determination in environmental waters. A large number of studies have been developed on this topic in reason of the importance of their monitoring in the studies of environmental mobility and potential degradation pathways. Every step of the analysis has been carefully considered, with a particular attention to sample preparation, in relationship with the problems involved in the analysis of real matrices. The different strategies to minimise interference from organic matter and to achieve optimal sensitivity, especially important in those samples with lower FQ concentrations, were also highlighted. Results and progress in this field have been described and critically commented. Moreover, a worldwide overview on the presence of FQs in the environmental waters has been reported

Haematic silicon in drowning

The aim of this paper was to evaluate silicon (Si) concentration in human whole ventricular blood as a further potential chemical marker in the diagnosis of drowning. We employed an acidic digestion for the extraction of soluble Si, and an alkaline digestion for the determination of total Si, including particulate matter, both arising from drowning medium. 29 suspected drowning situations, 24 in fresh water (Fw) and 5 in seawater (Sw), were examined. The difference in Si concentration between the left and right ventricular blood (Si DLeR) was measured and alkaline Si DLeR seems, indeed, a potentially significant complementary tool in the diagnosis of Fw drowning, because insoluble silicon fraction does not undergo hemo-dilution or hemo-concentration, and the DLeR is not affected by exogenous factors. In spite of the limited number of cases investigated, a good correlation was observed between the analytical results and the macro-microscopic autoptic findings

Simultaneous Pre-Concentration and HPLC-MS/MS Quantification of Phycotoxins and Cyanotoxins in Inland and Coastal Waters

The purpose of this study was to set up a sensitive method for the simultaneous determination of phycotoxins and cyanotoxins—Emerging pollutants with different structures and harmful properties (hepatotoxicity, neurotoxicity and cytotoxicity)—In environmental waters. Due to the low concentrations detected in these samples, a pre-concentration step is required and here it was performed in a single step with a commercial cartridge (Strata™-X), achieving enrichment factors up to 200 and satisfactory recovery (R = 70–118%) in different aqueous matrices. After solid-phase extraction (SPE), toxins were separated and quantified by High Performance Liquid Chromatography- Heated ElectroSpray Ionisation Tandem Mass Spectrometry (HPLC-HESI-MS/MS) in Multiple Reaction Monitoring (MRM) mode. An analytical evaluation of the proposed method was done based on the analytical figures of merit, such as precision and trueness, linearity, selectivity, and sensitivity, and it turned out to be a robust tool for the quantification of ng L−1 levels, phycotoxins and cyanotoxins in both freshwater and saltwater samples