Highly sensitive determination of 68 psychoactive pharmaceuticals, illicit drugs, and related human metabolites in wastewater by liquid chromatography–tandem mass spectrometry

The present work describes the development and validation of a highly sensitive analytical method for the simultaneous determination of 68 compounds, including illicit drugs (opiates, opioids, cocaine compounds, amphetamines, and hallucinogens), psychiatric drugs (benzodiazepines, barbiturates, anesthetics, antiepileptics, antipsychotics, antidepressants, and sympathomimetics), and selected human metabolites in influent and effluent wastewater (IWWand EWW) by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). The method involves a pre-concentration and cleanup step, carried out by solid-phase extraction (SPE) using the adsorbent Strata-XC, followed by the instrumental analysis performed by LC–MS/MS, using a Kinetex pentafluorophenyl (PFP) reversed-phase fused-core column and electrospray ionization (ESI) in both positive and negative modes. A systematic optimization of mobile phases was performed to cope with the wide range of physicochemical properties of the analytes. The PFP column was also compared with two reversed-phase columns: fused-core C18 and XBC18 (with a cross-butyl C18 ligand). SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g., matrix effects) have been also considered and discussed. Fragmentation patterns for all the classes were proposed. The validated method provides absolute recoveries between 75 and 120 % for most compounds in IWW and EWW. Low method limits of detection were achieved (between 0.04 and 10.0 ng/L for 87 % of the compounds), allowing a reliable and accurate quantification of the analytes at trace level. The method was successfully applied to the analysis of these compounds in five wastewater treatment plants in Santorini, a touristic island of the Aegean Sea, Greece. Thirty-two out of 68 compounds were detected in all IWW samples in the range between 0.6 ng/L (for nordiazepam) and 6,822 ng/L (for carbamazepine) and 22 out of 68 in all EWW samples, with values between 0.4 ng/L (for 9-OH risperidone) and 2,200 ng/L (for carbamazepine). The novel methodology described herein maximizes the information on the environmental analysis of these substances and also provides a first profile of 68 drugs in a Greek touristic are

Targeted Multiresidue Method for the Analysis of Different Classes of Pesticides in Agro-Food Industrial Sludge by Liquid Chromatography Tandem Mass Spectrometry

Sludge generated after washing of fruits and vegetables during agro-food processes is a complex matrix and selective methods for the identification and quantification of pesticides’ residues are necessary in order to achieve a sustainable and effective management of the total sewage. The present work describes the development and validation of a reliable, simple and fast analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of 47 pesticides of different chemical classes, including organosphosphates, pyrethroids, neonicotinoids, triazoles and others, in sludge samples after QuEChERS sample preparation. The necessity of the individual steps of QuEChERS was investigated and the LC-ESI-MS/MS conditions were optimized to achieve maximum sensitivity of the target analytes. The method limits of detection (LODs) ranged between 0.0005 mg/kg (imidacloprid) and 0.05 mg/kg (beta cyfluthrin). The recoveries ranged between 71–120% and the repeatability of the method was ≤25% expressed as relative standard deviation. The method was applied to sludge samples generated after washing of fruits in an agro-fruit-packaging unit in Greece. The results showed the presence of 37 pesticides’ active substances with concentrations ranging from low ppbs, such as fludioxinil (5 μg/kg) up to low ppms such as beta cyfluthrin (3.5 mg/kg) and with their sum concentration reaching up to 19 mg/kg

Targeted Multiresidue Method for the Analysis of Different Classes of Pesticides in Agro-Food Industrial Sludge by Liquid Chromatography Tandem Mass Spectrometry

Sludge generated after washing of fruits and vegetables during agro-food processes is a complex matrix and selective methods for the identification and quantification of pesticides’ residues are necessary in order to achieve a sustainable and effective management of the total sewage. The present work describes the development and validation of a reliable, simple and fast analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of 47 pesticides of different chemical classes, including organosphosphates, pyrethroids, neonicotinoids, triazoles and others, in sludge samples after QuEChERS sample preparation. The necessity of the individual steps of QuEChERS was investigated and the LC-ESI-MS/MS conditions were optimized to achieve maximum sensitivity of the target analytes. The method limits of detection (LODs) ranged between 0.0005 mg/kg (imidacloprid) and 0.05 mg/kg (beta cyfluthrin). The recoveries ranged between 71–120% and the repeatability of the method was ≤25% expressed as relative standard deviation. The method was applied to sludge samples generated after washing of fruits in an agro-fruit-packaging unit in Greece. The results showed the presence of 37 pesticides’ active substances with concentrations ranging from low ppbs, such as fludioxinil (5 μg/kg) up to low ppms such as beta cyfluthrin (3.5 mg/kg) and with their sum concentration reaching up to 19 mg/kg

Development and validation of a high-throughput headspace solid-phase microextraction gas chromatography-mass spectrometry methodology for target and suspect determination of honey volatiles

The determination of volatile compounds is essential for the chemical characterisation of honey's aroma and its correlation to its sensory profile and botanical origin. The present study describes the development, optimization and validation of a new, simple and reliable method for the determination of volatile compounds in honey using headspace solid-phase microextraction combined with gas chromatography/mass spectrometry (HS-SPME-GC-MS). The optimization of the SPME conditions showed that the ratio of honey: water (2:1) and the incubation temperature (60 °C) are the most critical parameters. Gas chromatography was performed with medium polar Varian CP-Select 624 column and the experimental Retention Index for a number of compounds was determined as an additional identification feature for suspect analysis. The simultaneous use of four internal standards chlorobenzene, benzophenone, 2-pentanol and 4-methyl-2-pentanone and matrix matched calibration enhanced method accuracy achieving recoveries 73–114 % and repeatability ranging between 3.9 and 19 % relative standard deviations. Furthermore, the superiority of the HS-SPME to static head space technique was verified exhibiting four-to nine-fold higher sensitivity. Target and suspect screening were applied to 30 Greek honey samples and 53 volatile compounds belonging to different chemical classes, such as alkanes, aldehydes, ketones, alcohols, and esters were identified with quantified concentrations ranging between 3.1 μg kg−1 (Limonene) up to 20 mg kg−1 (Benzeneacetaldehyde). Among the new findings is the detection of Myrtenol in Greek pine honey and 2,3-butanediol in Greek oak honey. The developed analytical protocol can be a valuable tool in order to chemically characterize honey based on the volatile content

Reflection of Socioeconomic Changes in Wastewater: Licit and Illicit Drug Use Patterns

The economic crisis plaguing Greece was expected to impact consumption of pharmaceuticals and illicit drugs – <i>a priori</i> to an unknown extent. We quantified the change of use for various classes of licit and illicit drugs by monitoring Athens’ wastewater from 2010 to 2014. A high increase in the use of psychoactive drugs was detected between 2010 and 2014, especially for antipsychotics (35-fold), benzodiazepines (19-fold), and antidepressants (11-fold). This directly reflects the perceived increase of incidences associated with mental illnesses in the population, as a consequence of severe socioeconomic changes. Other therapeutic classes, like antiepileptics, hypertensives, and gastric and ulcer drugs also showed an increase in use (from 2-fold increase for antiepileptics to 13-fold for hypertensives). In contrast, the overall use of antibiotics and NSAIDs decreased. For mefenamic acid, an almost 28-fold decrease was observed. This finding is likely related to the reduction in drug expenditure applied in public health. A 2-fold increase of methamphetamine use was detected, associated with a cheap street drug called ″<i>sisa</i>″ (related to marginal conducts), which is a health concern. MDMA (5-fold) and methadone (7-fold) use showed also an increase, while cocaine and cannabis estimates did not show a clear trend