Determination of Multiclass Pharmaceutical Residues in Milk Using Modified QuEChERS and Liquid-Chromatography-Hybrid Linear Ion Trap/Orbitrap Mass Spectrometry: Comparison of Clean-Up Approaches and Validation Studies.

A multi-residue method was developed to identify and quantify pharmaceutical drug residues in full-fat milk, using a modified QuEChERS extraction procedure and sonication combined with Ultra-High-Performance Liquid Chromatography-High-Resolution Orbitrap Mass Spectrometry (UHPLC-HR-Orbitrap-MS). Sample preparation involves three different QuEChERS extraction procedures and sorbents for the purification step. The optimized modified extraction method, combined with the clean-up approaches using C18 and the EMR-Lipid sorbent, has been validated in terms of linearity, recovery, precision, LOD and LOQ, matrix effects (ME) and expanded uncertainty.

Beneficial properties of Drimia numidica leaf methanolic extract against the cytogenotoxic effects of mitomycin C on human lymphocytes.

This study investigated the phytochemical profile of Drimia numidica leaf methanolic extract, as well as its cyto-genotoxic and cyto/genoprotective potential against mitomycin C (MMC) mediated effects on healthy human lymphocytes. Photosynthetic pigments, trace elements, and secondary metabolites were estimated and/or identified in methanolic extract of mature leaves, and the latter was further used for assessing its in vitro biological effects on MMC-free and/or MMC-treated human lymphocytes (at low, non-toxic concentrations of 0.001 and 0.

Enhancing bioactive compounds accumulation in red beet (Beta Vulgaris L.) plants by managing N nutrition. The identification of the 'critical' zone as a cultivation technique.

The increasing interest in natural health-promoting compounds, which are mostly plant secondary metabolites, inspired attempts to stimulate mechanisms strengthening their bioaccumulation in crop plants via abiotic stress while maintaining the yield potential. This study investigates the long-term effects of limiting nitrogen (N) supply on the concentration of total phenolics, free radical activity of natural antioxidants, betacyanin content, biomass production, net photosynthetic rate, total chlorophyll content, and plant water relations in red beetroot plants (Beta vulgaris L.) grown hydroponically.

Assessment of genetic effects and pesticide exposure of farmers in NW Greece.

The present study aims at evaluating potential genotoxic and cytotoxic effects caused by the occupational exposure of farmers to pesticide mixtures in the Aitoloakarnania Prefecture (Greece). The aforementioned assessment was conducted through in vivo Cytokinesis Block Micronucleus assay (CBMN assay) in peripheral blood lymphocytes, in relation to chemical analysis of pesticide residues in blood samples. The exposure of the farmers' population studied to different combinations of pesticides induced significant differences in the frequencies of micronuclei (MN) compared to those of the control group.

Assessing the human risk and the environmental fate of pharmaceutical Tramadol.

Tramadol (TRA) is a widely used human pharmaceutical and a well-established emerging pollutant and its potential genotoxic and cytotoxic effects on humans as well as its fate in aqueous systems demand full investigation. The present study is a multidisciplinary approach and provides important insights on the potential risks of Tramadol on humans accompanied by its photolytic transformation under simulated solar irradiation. The present study revealed that Tramadol can induce genotoxic and cytotoxic effects under the specific experimental conditions, significantly depended on the tested concentration.

Assessment of the toxic potential of rainwater precipitation: First evidence from a case study in three Greek cities.

Considering the necessity to monitor rainwater quality and the limited existing data regarding wet precipitations' toxic potential, the toxic potential of rainwater (RW) samples collected in three cities of Western Greece (Corfu, Agrinion and Patras) during May, October, November, and December of 2014 were investigated. The relationship of the adverse effects obtained, against cytokinesis block micronucleus (CBMN) and Vibrio fischeri bioluminescence (Microtox) assays with the physicochemical characteristics, the heavy metal concentration levels of rainwater samples and the meteorological parameters governing the climatic conditions in each region, were studied in detail. All samples showed pH values in the range of 5.

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions.

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.

Photocatalytic degradation kinetics, mechanism and ecotoxicity assessment of tramadol metabolites in aqueous TiO2 suspensions.

This study investigated for the first time the photocatalytic degradation of three well-known transformation products (TPs) of pharmaceutical Tramadol, N-desmethyl-(N-DES), N,N-bidesmethyl (N,N-Bi-DES) and N-oxide-tramadol (N-OX-TRA) in two different aquatic matrices, ultrapure water and secondary treated wastewater, with high (10 mg L(-1)) and low (50 μg L(-1)) initial concentrations, respectively. Total disappearance of the parent compounds was attained in all experiments. For initial concentration of 10 mg L(-1), the target compounds were degraded within 30-40 min and a mineralization degree of more than 80% was achieved after 240 min of irradiation, while the contained organic nitrogen was released mainly as NH4(+) for N-DES, N,N-Bi-DES and NO3(-) for N-OX-TRA.

Environmental fate of the insecticide cypermethrin applied as microgranular and emulsifiable concentrate formulations in sunflower cultivated field plots.

A field dissipation and transport study of the insecticide cypermethrin applied as microgranular (MG) and emulsifiable concentrate (EC) formulations has been conducted in field sunflower cultivations and bare soil plots with two different slopes (1% and 5%). The dissipation of insecticide in soil (on planting rows) was monitored for a period of 193 days. Cypermethrin residual concentrations in the upper soil layer (0-10 cm), 2 days after soil application (DASA), ranged from 0.

Spatiotemporal variation and risk assessment of pesticides in water of the lower catchment basin of Acheloos River, Western Greece.

A three-year monitoring survey (March 2005-February 2008) was conducted to investigate, on monthly basis, the presence of thirty pesticides belonging to various categories and metabolites, in Acheloos River (Western Greece), one of the most important water resources in Greece. Six sampling stations along the river were established. Water analyses were performed using solid-phase extraction combined with gas chromatography with flame thermionic detector and mass spectrometry.

Persistence of oxyfluorfen in soil, runoff water, sediment and plants of a sunflower cultivation.

A field dissipation and transport study of oxyfluorfen in a sunflower cultivation under Mediterranean conditions have been conducted in silty clay plots (cultivated and uncultivated) with two surface slopes (1% and 5%). The soil dissipation and transport of oxyfluorfen in runoff water and sediment, as well as the uptake by sunflower plants, were investigated over a period of 191 days. Among different kinetic models assayed, soil dissipation rate of oxyfluorfen was better described by first-order kinetics.

Environmental behavior of the fungicide metalaxyl in experimental tobacco field.

The loss of metalaxyl, a systemic fungicide, was determined in runoff water from loamy soil plots of various surface slopes cultivated with tobacco, over a period of 170 days. Conditions were selected to simulate agricultural practices employed in the Mediterranean region. The surface slopes of plots were 0, 2.

Lecithostaphylus tylosuri sp. nov. (Digenea, Zoogonidae) from the digestive tract of the needlefish Tylosurus acus imperialis (Teleostei, Belonidae).

Lecithostaphylus tylosuri sp. nov. (Digenea, Zoogonidae) specimen were collected from the digestive tract of Tylosurus acus imperialis (Teleostei, Belonidae) caught off the eastern coast of Tunisia.

Novel imazethapyr detoxification applying advanced oxidation processes.

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O₃), and hydrogen peroxide tied to UV-irradiation (H₂O₂/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed.

Passive sampling of selected pesticides in aquatic environment using polar organic chemical integrative samplers.

Purpose: Polar chemical integrative samplers (POCIS) were examined for their sampling efficiency of 12 pesticides and one metabolite commonly detected in surface waters. Laboratory-based calibration experiments of POCISs were conducted. The determined passive sampling rates were applied for the monitoring of pesticides levels in Lake Amvrakia, Western Greece.

Pesticide inputs from the sewage treatment plant of Agrinio to River Acheloos, western Greece: occurrence and removal.

This work reports the occurrence and the removal of a wide spectrum of pesticides in municipal wastewaters from the Agrinio region, Greece. Analytical determination was carried out by means of solid-phase extraction followed by gas chromatography equipped with flame thermionic and mass spectrometric detection. The herbicides atrazine, alachlor, isoproturon, and s-metolachlor and the insecticides diazinon, methidathion, fenthion and chlorpyriphos, were more frequently detected in influent and effluent samples while they were also detected in river samples.

Occurrence and removal of fungicides in municipal sewage treatment plant.

This work reports the occurrence and the removal of widely used fungicides, in municipal sewage treatment plant receiving combined sewage discharges and operating with primary (mechanical), secondary (activated sludge) and tertiary (sand filtration and chlorination) treatments that are commonly applied in Greece. Target analytes included compounds belonging to triazoles and anilino-pyrimidines. Analytical determination in wastewaters and river water samples was carried out by means of solid-phase extraction followed by gas chromatography equipped with flame thermionic and mass spectrometric detection.

2-Hydroxypyridine photolytic degradation by 254 nm UV irradiation at different conditions.

The degradation and mineralisation of (400 mL, 3.15 mM) aqueous solutions of 2-hydroxypyridine (2-HPY), a primary intermediate formed during the photolytic degradation of 2-chloropyridine (2-CPY), 2-bromopyridine (2-BPY) and 2-iodopyridine (2-IPY), was studied at 50 degrees C, under 254 nm UV irradiation in a range of conditions. The rate of 2-HPY disappearance was found to heavily depend on agitation, dissolved oxygen, pH and hydroxyl radical scavenger presence.

Photolytic removal and mineralisation of 2-halogenated pyridines.

The photolytic destruction and mineralisation of 2-halogenated pyridines (2-HalPYs) was studied in a range of conditions by means of ultraviolet irradiation at 254 nm. In all cases pseudo-first order kinetics satisfactorily describe the degradation process. Key decomposition products were identified and primary reaction pathways are proposed.

Organophosphorus pesticide residues in Greek virgin olive oil: levels, dietary intake and risk assessment.

The occurrence of organophosphorus pesticide (OPs) and their metabolite residues was investigated in 167 samples of Greek virgin olive oil during a 2-year (2004-2005) sampling campaign. A total of 30.5% of samples contained detectable residues, although only one sample contained dimethoate residues above the maximum residue limit.

Screening method for organophosphorus insecticides and their metabolites in olive oil samples based on headspace solid-phase microextraction coupled with gas chromatography.

This work is focused on the effectiveness of headspace solid-phase microextraction (HS-SPME) for the analysis of nine organophosphorus (OPs) insecticides (dimethoate, diazinon, fenitrothion, malathion, fenthion, parathion ethyl, methyl bromophos, methidathion, ethion) and four metabolites (omethoate, malaoxon, fenthion sulfoxide and fenthion sulfone) residues in olive oil samples. The efficiency of six fibre types with different film thickness was compared. PDMS (100 microm) was found to be the most suitable fibre for the analysis of OPs in olive oils.

Effects of dissolved carboxylates and carbonates on the adsorption properties of thiuram disulfate pesticides.

The adsorption of thiram and disulfiram onto alpha-Al2O3 and montmorillonite clay has been studied in the presence of small carboxylate anions, bicarbonate, formate, and oxalate. At natural concentrations, HCO3- enhances dramatically the adsorption of both pesticides on alpha-Al2O3 and clay. An analogous significant enhancement of pesticide adsorption is also observed in the presence of formate and oxalate.

Accumulation profiles of persistent organochlorines in liver and fat tissues of various waterbird species from Greece.

Waterbirds are particularly subject to accumulation of persistent organic pollutants (POPs) that have been shown to constitute a major hazard for this group of birds. Liver and fat tissue from ten species belonging to the orders Ciconiformes (Ardeidae, Ciconiidae, Phoenicopteridae) and Pelicaniformes (Pelecanidae, Phalacrocoracidae) were used as bioindicators in order to assess environmental pollution by POPs (HCHs, DDTs, cyclodienes, PCBs) in Greek wetlands. To our knowledge, this is the first study on POPs in livers of water birds in Greece and Eastern Mediterranean area.

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels.

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides.