•Emerging contaminant removal technologies have been summarized.•MBR, microalgae and activated sludge are effective biological removal processes.•Ozonation/H2O2 and photo-Fenton are highly effective ...chemical removal processes.•Many hybrid systems have enhanced removal capacity of emerging contaminants.•Future research regarding emerging contaminant removal has been proposed.
This review focuses on the removal of emerging contaminants (ECs) by biological, chemical and hybrid technologies in effluents from wastewater treatment plants (WWTPs). Results showed that endocrine disruption chemicals (EDCs) were better removed by membrane bioreactor (MBR), activated sludge and aeration processes among different biological processes. Surfactants, EDCs and personal care products (PCPs) can be well removed by activated sludge process. Pesticides and pharmaceuticals showed good removal efficiencies by biological activated carbon. Microalgae treatment processes can remove almost all types of ECs to some extent. Other biological processes were found less effective in ECs removal from wastewater. Chemical oxidation processes such as ozonation/H2O2, UV photolysis/H2O2 and photo-Fenton processes can successfully remove up to 100% of pesticides, beta blockers and pharmaceuticals, while EDCs can be better removed by ozonation and UV photocatalysis. Fenton process was found less effective in the removal of any types of ECs. A hybrid system based on ozonation followed by biological activated carbon was found highly efficient in the removal of pesticides, beta blockers and pharmaceuticals. A hybrid ozonation-ultrasound system can remove up to 100% of many pharmaceuticals. Future research directions to enhance the removal of ECs have been elaborated.
COVID-19 pandemic spread rapidly worldwide with unanticipated effects on mental health, lifestyle, stability of economies and societies. Although many research groups have already reported SARS-CoV-2 ...surveillance in untreated wastewater, only few studies evaluated the implications of the pandemic on the use of chemicals by influent wastewater analysis. Wide-scope target and suspect screening were used to monitor the effects of the pandemic on the Greek population through wastewater-based epidemiology. Composite 24 h influent wastewater samples were collected from the wastewater treatment plant of Athens during the first lockdown and analyzed by liquid chromatography mass spectrometry. A wide range of compounds was investigated (11,286), including antipsychotic drugs, illicit drugs, tobacco compounds, food additives, pesticides, biocides, surfactants and industrial chemicals. Mass loads of chemical markers were estimated and compared with the data obtained under non-COVID-19 conditions (campaign 2019). The findings revealed increases in surfactants (+196%), biocides (+152%), cationic quaternary ammonium surfactants (used as surfactants and biocides) (+331%), whereas the most important decreases were estimated for tobacco (−33%) and industrial chemicals (−52%). The introduction of social-restriction measures by the government affected all aspects of life.
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•Findings reflect the effects of pandemic and social distancing.•Wastewater-based epidemiology was used to assess the exposure to various chemicals.•Significant changes in illicit drug consumption were observed.•Surfactants and biocides showed a notable increase 196% and 152%, respectively.•Significant reduction of the industrial chemicals (52%) due to business closure
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•Three new tR prediction models were developed for RPLC and HILIC platforms.•Mote Carlo sampling method was developed to facilitate suspect and non-target screening.•tR prediction was ...useful in the identification of 10 new TPs of emerging contaminants.•A comprehensive database of 273 biocides was built and used for this study.•28 biocides in total were detected in treated wastewater and sludge of Athens.
Hydrophilic interaction liquid chromatography (HILIC) and reversed phase LC (RPLC) coupled to high resolution mass spectrometry (HRMS) are widely used for the identification of suspects and unknown compounds in the environment. For the identification of unknowns, apart from mass accuracy and isotopic fitting, retention time (tR) and MS/MS spectra evaluation is required. In this context, a novel comprehensive workflow was developed to study the tR behavior of large groups of emerging contaminants using Quantitative Structure-Retention Relationships (QSRR). 682 compounds were analyzed by HILIC-HRMS in positive Electrospray Ionization mode (ESI). Moreover, an extensive dataset was built for RPLC-HRMS including 1830 and 308 compounds for positive and negative ESI, respectively. Support Vector Machines (SVM) was used to model the tR data. The applicability domains of the models were studied by Monte Carlo Sampling (MCS) methods. The MCS method was also used to calculate the acceptable error windows for the predicted tR from various LC conditions. This paper provides validated models for predicting tR in HILIC/RPLC-HRMS platforms to facilitate identification of new emerging contaminants by suspect and non-target HRMS screening, and were applied for the identification of transformation products (TPs) of emerging contaminants and biocides in wastewater and sludge.
Food fraud, being the act of intentional adulteration of food for financial advantage, has vexed the consumers and the food industry throughout history. According to the European Committee on the ...Environment, Public Health and Food Safety, fruit juices are included in the top 10 food products that are most at risk of food fraud. Therefore, reliable, efficient, sensitive and cost-effective analytical methodologies need to be developed continuously to guarantee fruit juice quality and safety. This review covers the latest advances in the past ten years concerning the targeted and non-targeted methodologies that have been developed to assure fruit juice authenticity and to preclude adulteration. Emphasis is placed on the use of hyphenated techniques and on the constantly-growing role of MS-based metabolomics in fruit juice quality control area.
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•A novel multi-residue determination of veterinary drugs in food is presented.•A thorough sample preparation optimization for all the compounds was performed.•Validation data and ...applications in milk, egg, butter and fish samples are provided.•Successful proficiency testing verified the applicability of the developed method.
A simple and sensitive multi-residue method for the determination of 115 veterinary drugs and pharmaceuticals, belonging in more than 20 different classes, in butter, milk powder, egg and fish tissue has been developed. The method involves a simple generic solid–liquid extraction step (solvent extraction, SE) with 0.1% formic acid in aqueous solution of EDTA 0.1% (w/v)–acetonitrile (ACN)–methanol (MeOH) (1:1:1, v/v) with additional ultrasonic-assisted extraction. Precipitation of lipids and proteins was promoted by subjecting the extracts at very low temperature (−23°C) for 12h. Further cleanup with hexane ensures fat removal from the matrix. Analysis was performed by liquid chromatography coupled with electrospray ionization and tandem mass spectrometry (LC-ESI-MS/MS). Two separate runs were performed for positive and negative ionization in multiple reaction monitoring mode (MRM). Particular attention was devoted to extraction optimization: different sample-to-extracting volume ratios, different concentrations of formic acid in the extraction solvent and different ultrasonic extraction temperatures were tested in butter, egg and milk powder samples. The method was also applied in fish tissue samples. It was validated, on the basis of international guidelines, for all four matrices. Quantitative analysis was performed by means of standard addition calibration. For over 80% of the analytes, the recoveries were between 50% and 120% in all matrices studied, with RSD values in the range of 1–18%. Limits of detection (LODs) and quantification (LOQs) ranged from 0.008μgkg−1 (oxfendazole in butter) to 3.15μgkg−1 (hydrochlorthiazide in egg). The evaluated method provides reliable screening, quantification, and identification of 115 veterinary drug and pharmaceutical residues in foods of animal origin and has been successfully applied in real samples.
The occurrence and spatial distribution of 158 pharmaceuticals and drugs of abuse were studied in seawater of the Eastern Mediterranean Sea (Saronikos Gulf and Elefsis Bay in central Aegean Sea). ...This area is affected by various anthropogenic pressures as it receives the treated wastewater of the greatest Athens area and off-shore input fluxes. This study constitutes the largest one in terms of number of analytes in this environmental compartment. It provides the first evidence on the occurrence of several pharmaceuticals in marine environment including amoxicillin, lidocaine, citalopram or tramadol, among others.
22 samples were collected at three different depths in 9 sampling stations in order to assess the presence and the spatial distribution of the target compounds. A multi-residue method based on solid phase extraction and liquid chromatography coupled to tandem mass spectrometry was developed for the determination of the 158 target substances and validated for seawater sample analysis. 38 out of the 158 target compounds were detected, 15 of them with frequencies of detection equal to or higher than 50%. The highest detected values corresponded to amoxicillin, caffeine and salicylic acid, with concentrations in the range of <5.0–127.8ngL−1; 5.2–78.2ngL−1 and <0.4–53.3ngL−1, respectively. Inputs from the wastewater treatment plant (WWTP) of Athens revealed to be the main source of pollution in the Inner Saronikos Gulf, whereas, other anthropogenic pressures such as contamination from shipping activity, industrial effluents, dredging and/or inputs from land proved to be also relevant. Τhe concentrations of some compounds varied significantly with depth suggesting that currents play an important role in the dilution of the target compounds.
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•This is the largest study of emerging contaminants (158) in seawater.•Thirty eight compounds have been detected.•Amoxicillin, salicylic acid and caffeine showed the highest concentration levels.•Wastewater release proved to be the major source of contamination.
Since 2019, Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), impaired public health with considerable morbidity and mortality due to the lack of vaccines and effective treatment. The ...severe disease mainly harmed adults with predisposing medical comorbidities (such as heart disease, hypertension, chronic lung disease), while it can occur in healthy individuals that may be asymptomatic. Wastewater-based Epidemiology (WBE), a non-invasive, objective, chemical tool was used to monitor and estimate the changes in drug's consumption and prescription patterns under normal conditions (2019) and under COVID-19 pandemic conditions (2020). NSAIDs, antihypertensives, diuretics, antiepileptics, antilipidemics, antibiotics, analgesics, antivirals, anticancer drugs, contrast iodinated drugs, antidiabetics, antiallergic drugs, antiulcers and other pharmaceuticals were studied in wastewater and revealed the application of various treatments during the first wave of the pandemic in Athens, Greece. Data were correlated with COVID-19 infection therapeutical plans. The result of the analysis revealed a remarkable increase for antiviral drugs (170%), hydroxychloroquine (387%), and antibiotics (57%), which were the most applied treatments against COVID-19 during the first wave in Greece. In agreement with related authorities urge, NSAIDs presented decrease (27%) during the first lockdown, while paracetamol demonstrated a remarkable increase (198%). The use levels for Angiotensin II receptor blockers such as valsartan, and co-administrated diuretics, such as hydrochlorothiazide, were reduced during 2020, by 32% and 26% respectively.
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•Significant increase was observed for antiviral drugs (170%) and paracetamol (198%).•Hydroxychloroquine consumption showed a 387% increase during lockdown.•The consumption levels for hypertensive agents were reduced in 2020.•Antibiotics demonstrated a noteworthy increase (57%).•NSAIDs consumption showed a 27% decrease during lockdown.
Fig fruit (Ficus carica L.) is one of the most important agricultural products of the tropic and subtropics areas. In the Middle East and the Mediterranean region, the fig is included in diet since ...the ancient years and it is considered as the symbol of longevity. This review presents the main phytochemical compounds found in fresh and dried figs of different varieties, describes the analytical methods used for their determination and discuss the antioxidant capacity and the potential effects of figs in human health. Phenolic acids and flavonoids are the major types of phytochemical compounds that have been found in fresh and dried figs. Their levels are strongly influenced by various factors such as the color, the part of fruit, the maturity and the drying process. Gallic acid, chlorogenic acid, rutin, quercetin-3-O-rutinoside and epicatechin are the most predominant phenolic acids and flavonoids in dried and fresh fig varieties. Extracts of dark-colored varieties contain higher amount of phenolic compounds than the light-colored varieties. Fruit skin contributes most to the amount of phenolic compounds compared to the fruit pulp. The ripening stage affects the concentrations of phenolic compounds in figs, the maximum have been found in ripe fruit. On the other hand, contradictory results have been reported in the literature regarding the effect of air- and sun- drying on the total content of phytochemical compounds, as well as on the concentrations of individual phenolic compounds and carotenoids in figs. The antioxidant capacity of figs is highly correlated with their amount of phenolic compounds. The leaves, roots, fruit and latex of the plant are known for their health properties including acetyl cholinesterase inhibition, antifungal, anti-helminthic and anticarcinogenic activities. Future efforts should be focused on the application of fig extracts as functional ingredients of food products, on clinical trials in order to confirm the beneficial effect of plant extracts in human health and, on the valorization of the waste material produced during figs' processing.
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•Phenolic acids and flavonoids are the main phytochemical compounds found in figs.•Colorimetric and chromatographic methods have been used for their determination.•Dark-colored, unpeeled, dried figs have the highest content of phenolic compounds.•Ripening and drying processes affect figs' phytochemical composition.•In vitro studies show protective effects of fig and leaf extracts against some diseases.
There is a growing need for indexing and harmonizing retention time (tR) data in liquid chromatography derived under different conditions to aid in the identification of compounds in high resolution ...mass spectrometry (HRMS) based suspect and nontarget screening of environmental samples. In this study, a rigorously tested, inexpensive, and simple system-independent retention index (RI) approach is presented for liquid chromatography (LC), based on the cocamide diethanolamine homologous series (C(n = 0–23)-DEA). The validation of the CDEA based RI system was checked rigorously on eight different instrumentation and LC conditions. The RI values were modeled using molecular descriptor free technique based on structural barcoding and convolutional neural network deep learning. The effect of pH on the elution pattern of more than 402 emerging contaminants were studied under diverse LC settings. The uncertainty associated with the CDEA RI model and the pH effect were addressed and the first RI bank based on CDEA calibrants was developed. The proposed RI system was used to enhance identification confidence in suspect and nontarget screening while facilitating successful comparability of retention index data between various LC settings. The CDEA RI app can be accessed at https://github.com/raalizadeh/RIdea.
The information obtained from the chemical analysis of specific human excretion products (biomarkers) in urban wastewater can be used to estimate the exposure or consumption of the population under ...investigation to a defined substance. A proper biomarker can provide relevant information about lifestyle habits, health and wellbeing, but its selection is not an easy task as it should fulfil several specific requirements in order to be successfully employed. This paper aims to summarize the current knowledge related to the most relevant biomarkers used so far. In addition, some potential wastewater biomarkers that could be used for future applications were evaluated. For this purpose, representative chemical classes have been chosen and grouped in four main categories: (i) those that provide estimates of lifestyle factors and substance use, (ii) those used to estimate the exposure to toxicants present in the environment and food, (iii) those that have the potential to provide information about public health and illness and (iv) those used to estimate the population size. To facilitate the evaluation of the eligibility of a compound as a biomarker, information, when available, on stability in urine and wastewater and pharmacokinetic data (i.e. metabolism and urinary excretion profile) has been reviewed. Finally, several needs and recommendations for future research are proposed.
•Wastewater biomarkers provide information on lifestyle habits, health and wellbeing.•Specific criteria should be followed to select a suitable biomarker.•Report of the current knowledge of the most relevant biomarkers used so far•Proposal of potential wastewater biomarkers for future applications•Review of pharmacokinetic data and stability in urine and wastewater for each biomarker
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