Evaluation of Contaminants of Emerging Concern and Their Transformation Products in Water

In recent decades, pharmaceuticals have emerged as a significant new group of contaminants of emerging concern (CECs). Due to their inefficient removal by conventional wastewater treatment plants (WWTPs), a significant amount of these drugs enters the aquatic environment via municipal sewage systems. Despite the recent consumption trend, which is projected to continue in the future due to rising incidence of health issues requiring pharmaceutical treatment, little is known about the occurrence and fate of many pharmaceuticals in the aquatic environment. This thesis studied ten pharmaceuticals for which there is a considerable lack of data concerning their occurrence and fate in the aquatic environment. Thus, new analytical methods have been developed and validated for the determination of CECs and their transformation products (TPs). As a result, nine new TPs of two drugs (irinotecan and aliskiren) in water have been identified using UHPLC and mass spectrometry (QTRAP and Orbitrap). Moreover, a fully automated online SPE LC MS/MS method was validated for the determination ten pharmaceuticals in wastewater, allowing ultra-trace analysis. In addition to these targeted methods, the potential of LC-HRMS was explored for non-target screening of wastewater and surface waters from Greece, France, and Italy. A total of 264 environmental contaminants were identified and the findings were deposited into the NORMAN databases using the Suspect List Exchange and Digital Sample Freezing Platform. Finally, experimental design (DOE) techniques were applied to optimize and study the robustness of CECs’ abatement processes. Thus, the effects of various factors were studied on the solar photodegradation of irinotecan and the UV photocatalytic degradation of maprotiline. Consequently, WWTP operational guidelines have been established by identifying the factors that have no effect, or those that must be strictly controlled, as even tiny alterations can result in decreased efficiency

A Fully Automated Online SPE-LC-MS/MS Method for the Determination of 10 Pharmaceuticals in Wastewater Samples

The increasing use of pharmaceuticals, their presence in the aquatic environment, and the associated toxic effects, have raised concerns in recent years. In this work, a new multi-residue analytical method was developed and validated for the determination of 10 pharmaceuticals in wastewaters using online solid-phase extraction (online SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds included in the method were antineoplastics (cabazitaxel, docetaxel, doxorubicin, etoposide, irinotecan, methotrexate, paclitaxel, and topotecan), renin inhibitors (aliskiren), and antidepressants (maprotiline). The method was developed through several experiments on four online SPE cartridges, three reversed phase chromatography columns, and four combinations of mobile phase components. Under optimal conditions, very low limits of detection (LODs) of 1.30 to 10.6 ng L(−1) were obtained. The method was repeatable, with relative standard deviations (RSD, %) for intraday and interday precisions ranged from 1.6 to 7.8 and from 3.3 to 13.2, respectively. Recovery values ranged from 78.4 to 111.4%, indicating the reproducibility of the method. Matrix effects were mainly presented as signal suppression, with topotecan and doxorubicin being the two most affected compounds (31.0% signal suppression). The proposed method was successfully applied to hospital effluents, detecting methotrexate (4.7–9.3 ng L(−1)) and maprotiline (11.2–23.1 ng L(−1)). Due to the shorter overall run time of 15 min, including sample preparation, and reduced sample volume (0.9 mL), this on-line SPE-LC-MS/MS method was extremely convenient and efficient in comparison to the classical off-line SPE method. The proposed method was also highly sensitive and can be used for ultratrace quantification of the studied pharmaceuticals in wastewaters, providing useful data for effective environmental monitoring

Identification of Illicit Conservation Treatments in Fresh Fish by Micro-Raman Spectroscopy and Chemometric Methods

In the field of food control for fresh products, the identification of foods subjected to illicit conservation treatments to extend their shelf life is fundamental. Fresh fish products are particularly subjected to this type of fraud due to their high commercial value and the fact that they often have to be transported over a long distance, keeping their organoleptic characteristics unaltered. Treatments of this type involve, e.g., the bleaching of the meat and/or the momentary abatement of the microbial load, while the degradation process continues. It is therefore important to find rapid methods that allow the identification of illicit treatments. The study presented here was performed on 24 sea bass samples divided into four groups: 12 controls (stored on ice in the fridge for 3 or 24 h), and 12 treated with a Cafodos-like solution for 3 or 24 h. Muscle and skin samples were then characterized using micro-Raman spectroscopy. The data were pre-processed by smoothing and taking the first derivative and then PLS-DA models were built to identify short- and long- term effects on the fish's muscle and skin. All the models provided the perfect classification of the samples both in fitting and cross-validation and an analysis of the bands responsible for the effects was also reported. To the best of the authors' knowledge, this is the first time Raman spectroscopy has been applied for the identification of a Cafodos-like illicit treatment, focusing on both fish muscle and skin evaluation. The procedure could pave the way for a future application directly on the market through the use of a portable device

A Fully Automated Online SPE-LC-MS/MS Method for the Determination of 10 Pharmaceuticals in Wastewater Samples

The increasing use of pharmaceuticals, their presence in the aquatic environment, and the associated toxic effects, have raised concerns in recent years. In this work, a new multi-residue analytical method was developed and validated for the determination of 10 pharmaceuticals in wastewaters using online solid-phase extraction (online SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds included in the method were antineoplastics (cabazitaxel, docetaxel, doxorubicin, etoposide, irinotecan, methotrexate, paclitaxel, and topotecan), renin inhibitors (aliskiren), and antidepressants (maprotiline). The method was developed through several experiments on four online SPE cartridges, three reversed phase chromatography columns, and four combinations of mobile phase components. Under optimal conditions, very low limits of detection (LODs) of 1.30 to 10.6 ng L−1 were obtained. The method was repeatable, with relative standard deviations (RSD, %) for intraday and interday precisions ranged from 1.6 to 7.8 and from 3.3 to 13.2, respectively. Recovery values ranged from 78.4 to 111.4%, indicating the reproducibility of the method. Matrix effects were mainly presented as signal suppression, with topotecan and doxorubicin being the two most affected compounds (31.0% signal suppression). The proposed method was successfully applied to hospital effluents, detecting methotrexate (4.7–9.3 ng L−1) and maprotiline (11.2–23.1 ng L−1). Due to the shorter overall run time of 15 min, including sample preparation, and reduced sample volume (0.9 mL), this on-line SPE-LC-MS/MS method was extremely convenient and efficient in comparison to the classical off-line SPE method. The proposed method was also highly sensitive and can be used for ultratrace quantification of the studied pharmaceuticals in wastewaters, providing useful data for effective environmental monitoring

Content of major, minor and toxic elements of different edible mushrooms grown in Mekelle, Tigray, Northern Ethiopia

Major, minor and toxic elements were determined by flame atomic absorption spectrometry and flame photometry in edible canned, wild and cultivated oyster mushrooms grown in cotton waste, wheat straw and wood waste substrates in Mekelle, Tigray, Ethiopia. Dry ashing using mixtures of HNO3:H2SO4:H2O2 (1:1:1 ratio) was used for digestion. The mean concentrations (mg/kg) of the studied elements in the mushroom samples were ranged from 964.66 to 4180.33, 2652.66 to 19918.66, 22.00 to 34.64, 16.00 to 30.38, 34.13 to 621.06, 40.25 to 120.91, 8.40 to 34.33, 4.22 to 30.63, 1.94 to 2.52 and 1.53 to 2.17 for Na, K, Ca, Mg, Fe, Zn, Cu, Mn, Cd and Pb, respectively. There were significant differences (p < 0.05) in the K, Fe, Zn and Mn levels of the mushroom samples which may be attributed to substrate variations. Moreover, significantly high correlations were observed between Na-K, Ca-Cd, Fe-Mn, Zn-Cu, Zn-Pb, Cu-Pb and Cd-Pb. Most of the results of this study were in good agreement with WHO recommended limits. However, the concentrations of Na and Cd in canned mushroom and all elements grown in wood substrate were recorded above the WHO recommended limits. The results of this study showed that, with the exception of canned and wood waste grown, the mushrooms can be used for human diets because of their acceptable content of many essential and minor elements and low content of toxic metals

Enhanced Photocatalytic Activity of CuWO4 Doped TiO2 PhotocatalystTowards Carbamazepine Removal under UV Irradiation

Abatement of contaminants of emerging concerns (CECs) in water sources has been widely studied employing TiO2 based heterogeneous photocatalysis. However, low quantum energy yield among other limitations of titania has led to its modification with other semiconductor materials for improved photocatalytic activity. In this work, a 0.05 wt.% CuWO4 over TiO2 was prepared as a powder composite. Each component part synthesized via the sol-gel method for TiO2, and CuWO4 by co-precipitation assisted hydrothermal method from precursor salts, underwent gentle mechanical agitation. Homogenization of the nanopowder precursors was performed by zirconia ball milling for 2 h. The final material was obtained after annealing at 500 degrees C for 3.5 h. Structural and morphological characterization of the synthesized material has been achieved employing X-ray diffraction (XRD), Fourier transform infra-red (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) N-2 adsorption-desorption analysis, Scanning electron microscopy-coupled Energy dispersive X-ray spectroscopy (SEM-EDS), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis diffuse reflectance spectroscopy (UV-vis DRS) for optical characterization. The 0.05 wt.% CuWO4-TiO2 catalyst was investigated for its photocatalytic activity over carbamazepine (CBZ), achieving a degradation of almost 100% after 2 h irradiation. A comparison with pure TiO2 prepared under those same conditions was made. The effect of pH, chemical scavengers, H2O2 as well as contaminant ion effects (anions, cations), and humic acid (HA) was investigated, and their related influences on the photocatalyst efficiency towards CBZ degradation highlighted accordingly

Multi-Omics Approaches for Freshness Estimation and Detection of Illicit Conservation Treatments in Sea Bass (Dicentrarchus Labrax): Data Fusion Applications

: Fish freshness consists of complex endogenous and exogenous processes; therefore, the use of a few parameters to unravel illicit practices could be insufficient. Moreover, the development of strategies for the identification of such practices based on additives known to prevent and/or delay fish spoilage is still limited. The paper deals with the identification of the effect played by a Cafodos solution on the conservation state of sea bass at both short-term (3 h) and long-term (24 h). Controls and treated samples were characterized by a multi-omic approach involving proteomics, lipidomics, metabolomics, and metagenomics. Different parts of the fish samples were studied (muscle, skin, eye, and gills) and sampled through a non-invasive procedure based on EVA strips functionalized by ionic exchange resins. Data fusion methods were then applied to build models able to discriminate between controls and treated samples and identify the possible markers of the applied treatment. The approach was effective in the identification of the effect played by Cafodos that proved to be different in the short- and long-term and complex, involving proteins, lipids, and small molecules to a different extent