Characterization of scrubber water discharges from ships using comprehensive suspect screening strategies based on GC-APCI-HRMS.

An extended suspect screening approach for the comprehensive chemical characterization of scrubber discharge waters from exhaust gas cleaning systems (EGCSs), used to reduce atmospheric shipping emissions of sulphur oxides, was developed. The suspect screening was based on gas chromatography coupled with high-resolution mass spectrometry (GC-HRMS) and focused on the identification of polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives (alkyl-PAHs), which are among the most frequent and potentially toxic organic contaminants detected in these matrices. Although alkyl-PAHs can be even more abundant than parent compounds, information regarding their occurrence in scrubber waters is scarce. For compound identification, an in-house compound database was built, with 26 suspect groups, including 25 parent PAHs and 23 alkyl-PAH homologues. With this approach, 7 PAHs and 12 clusters of alkyl-PAHs were tentatively identified, whose occurrence was finally confirmed by target analysis using GC coupled with tandem mass spectrometry (GC-MS/MS). Finally, a retrospective analysis was performed to identify other relevant (poly)cyclic aromatic compounds (PACs) of potential concern in scrubber waters. According to it, 18 suspect groups were tentatively identified, including biphenyls, dibenzofurans, dibenzothiophenes and oxygenated PAHs derivatives. All these compounds could be used as relevant markers of scrubber water contamination in heavy traffic marine areas and be considered as potential stressors when evaluating scrubber water toxicity.

High resolution mass spectrometric suspect screening, wide-scope target analysis of emerging contaminants and determination of legacy pollutants in adult black-tailed godwit Limosa limosa limosa in the Netherlands - A pilot study.

The Dutch breeding population of the black-tailed godwit Limosa limosa limosa has declined substantially over recent decades; the role of contaminants is unknown. We analysed liver samples from 11 adult birds found dead on their breeding grounds in SW Friesland 2016-2020, six from extensive, herb-rich grasslands, five from intensive grasslands. We carried out LC and GC wide-scope target analysis of more than 2400 substances, LC suspect screening for more than 60,000 substances, target analysis for Cd, Hg, Ni and Pb, organo-phosphate flame retardants (OPFRs), dechlorane plus compounds and selected polybrominated diphenyl ether flame retardants (PBDEs), and bioassay for polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/PDBFs) and dioxin-like polychlorinated biphenyls (dl-PCBs). Residues of 29 emerging contaminants (ECs) were determined through wide-scope target analysis. Another 20 were tentatively identified through suspect screening. These contaminants include industrial chemicals (personal care products, surfactants, PAHs and others), plant protection products (PPPs) and pharmaceuticals and their transformation products. Total contaminant load detected by wide-scope target analysis ranged from c. 155 to c. 1400 ng g-1 and was generally lower in birds from extensive grasslands. Heatmaps suggest that birds from intensive grasslands have a greater mix and higher residue concentrations of PPPs, while birds from extensive grasslands have a greater mix and higher residue concentrations of per- and polyfluoroalkyl substances (PFAS). All four metals and two OPFRs were detected. All tested PBDEs were below the respective LODs. Bioassay revealed presence of PBDDs, PBDFs and dl-PCBs. Further research is required to elucidate potential health risks to godwits and contaminant sources.

Occurrence of pharmaceuticals in the wastewater of a Greek hospital: Combining consumption data collection and LC-QTOF-MS analysis.

In this article we applied drug consumption approach and chemical analysis in parallel to investigate the concentrations of a large number of pharmaceuticals in different streams of a General Hospital. Drugs consumption data was collected during two periods (Period 1, 2) and the predicted environmental concentrations (PECs) were estimated for the wastewater of a building housing specific medical services (Point A) and for the entire hospital (Point B). Hospital wastewater samples (HWW) samples were also collected from these points and periods and the measured environmental concentrations (MEC) were determined using UHPLC-ESI-QTOF-MS/MS. According to consumption data, the highest number of drugs was consumed in the departments of Hematology, Intensive Care Unit, Cardiology, Internal Medicine, and Oncology, while the number of active substances used in the hospital was 413 (Period 1) and 362 (Period 2). For most substances, much higher PEC and MEC values were found at the HWW of Point A indicating that on-site treatment of this stream could be examined in the future. The application of wide-scope target analysis allowed the quantification of 122 compounds, while 21 additional substances were identified using suspect screening. The highest mean concentrations in Period 1 were found for acetaminophen (1100 µg/L) and rifaximin (723 µg/L), while in Period 2 for iopromide (458 µg/L) and acyclovir (408 µg/L). Among the detected compounds, 19 metabolites were determined. Atenolol acid, 1-hydroxy-midazolam and clopidogrel carboxylic acid were quantified at concentrations much higher than parent compounds indicating the importance of metabolites' monitoring in HWW. Calculation of PEC/MEC ratio for 36 pharmaceuticals showed sufficient correlation of these values for 19 % to 33 % of the substances depending on the examined period and sampling point. The parallel collection of drugs consumption data and chemical analysis give a thorough picture of the substances present in HWW and their main sources, facilitating decision-making for their better management.

One-step extraction and analysis of 45 contaminants of emerging concern using QuEChERS methodology and HR-MS in radish leaves and roots.

The scarcity of freshwater has led to a considerable increase of the reuse of reclaimed wastewater for irrigation of field crops [1,2]. This practice potentially exposes agricultural produce to a large variety of xenobiotic compounds including contaminants of emerging concern (CECs) which have been widely recognized to be present in wastewater [3]. Common approaches for the extraction of CECs from crops rely on solid-liquid extraction [4], assisted solvent extraction [5], ultra-sound solvent extraction [6] and recently QuEChERS (QUick, Easy, CHeap, Effective, Rugged and Safe) [[7], [8]-9]. Here, eight QuEChERS-based methodologies were compared for their suitability to determine 45 CECs in roots and leaves of soil-grown radish. The key points of the method development were:•The development of two single-step analytical methods specific for radish root and leaves, after testing eight different approaches using QuEChERS extraction for the quantitation of 45 CECs. The analytical methodology selected requires minimal time and solvent, making it cost-effective.•Methods validation were performed at five concentrations levels (2, 5, 10, 50 and 200 ng g-1), with low limits of quantification between 0.01 and 0.32 ng g-1.•The two optimized methodologies may be applied to identify large number of compounds of different families in radish crop. However, validation will be needed to quantify compounds different from the target compounds of this paper.

Wide-scope target analysis of emerging contaminants in landfill leachates and risk assessment using Risk Quotient methodology.

Raw and treated leachate samples were collected from different landfills in Greece and analyzed for several groups of emerging contaminants using high resolution mass spectrometric workflows to investigate the possible threat from their discharge to the aquatic environment. Fifty-eight compounds were detected; 2-OH-benzothiazole was found at 84 % of the samples and perfluorooctanoic acid at 68 %. Bisphenol A, valsartan and 2-OH-benzothiazole had the highest average concentrations in raw leachates, after biological treatment and after reverse osmosis, respectively. In untreated leachates, Risk Quotients > 1 were calculated for 35 and 18 compounds when maximum and average concentrations were used, indicating an ecological threat for the aquatic environment. Leachates' biological treatment partially removed COD and NH4+-N, as well as 52.3 % of total emerging contaminants. The application of reverse osmosis resulted in a 98 % removal of major pollutants, 99 % removal of total emerging contaminants and a significant decrease of ecotoxicity to Lemna minor. Beside the decrease of the detected micropollutants during treatment, RQs > 1 were still calculated for 13 and 3 compounds after biological treatment and reverse osmosis, respectively. Among these, special attention should be given to 2-OH-benzothiazole and bisphenol A that had RQ values much higher than 1 for all tested organisms.

Chemometric determination of the shelf life of opened cans using the migration of specific metals as quality indicators.

The aim of this work is the evaluation of quality indicators for the estimation of the shelf life of opened cans using the migration of specific metals as variables. For this reason the determination of targeted analytes such as: Cd, Pb, As, Cu, Cr, Ni, Fe, Mn and Sn in different canned samples (cardoon, tuna, green and red beans, corn, and fungi) by Electrothermal Atomic Absorption Spectrometry (Perkin Elmer, SIMAA 6000) was developed and validated. Statistical analysis was performed using SPSS version 22. Principal component analysis (PCA) and cluster analysis were performed in order to examine the correlation between the content of metals and metalloids and the storage time of opened cans. The results showed that there is a strong correlation between metal concentration and storage time, especially for Fe and Sn. The storage time ranged from hours to days and the vast number of collected data sets, led to reliable conclusions about the evaluation of a new shelf life indicator. Principal component analysis indicated the appropriate storage time for opened cans, where no significant migration was observed.

UHPLC-QTOF MS screening of pharmaceuticals and their metabolites in treated wastewater samples from Athens.

After consumption, pharmaceuticals are excreted as parent compounds and/or metabolites in urine and faeces. Some are not completely removed during wastewater treatments, forcing sewage treatment plants (STPs) to apply alternative technologies to guarantee quality of treated water. To monitor the removal efficiency of STPs, not only unchanged compounds and metabolites have to be taken into account, but also formation of possible transformation products (TPs). In this work, QTOF MS has been used for screening metabolites/TPs of pharmaceuticals in effluent wastewater from Athens. A customised database was built with the exact masses of metabolites reported in literature for the parent drugs found in an initial screening. Additionally, TPs identified in previous degradation experiments performed at our laboratory were included. Up to 34 metabolites/TPs were detected for omeprazole, venlafaxine, clindamycin, clarithromycin, clopidogrel or dipyrone, among others. Seven corresponded to TPs whose reference standards were available at our lab, seven were TPs previously identified in laboratory degradation experiments, eight were TPs tentatively identified by QTOF MS without reference standards, and twelve TPs were discovered after using the common fragmentation pathway approach. Tentative identification of TPs was supported by prediction of their chromatographic retention time based on the use of advanced chemometric QSRR models.

Development, validation and accreditation of a method for the determination of Pb, Cd, Cu and As in seafood and fish feed samples.

A rapid, sensitive, accurate and precise method for the determination of Pb, Cd, As and Cu in seafood and fish feed samples by Simultaneous Electrothermal Atomic Absorption Spectrometry was developed in regard to Council Directive 333/2007EC and ISO/IEC 17025 (2005). Different approaches were investigated in order to shorten the analysis time, always taking into account the sensitivity. For method validation, precision (repeatability and reproducibility) and accuracy by addition recovery tests have been assessed as performance criteria. The expanded uncertainties based on the Eurachem/Citac Guidelines were calculated. The method was accredited by the Hellenic Accreditation System and it was applied for an 8 years study in seafood (n=202) and fish feeds (n=275) from the Greek market. The annual and seasonal variation of the elemental content and correlation among the elemental content in fish feeds and the respective fish samples were also accomplished.

Two-step derivatization procedures for the ionization enhancement of anabolic steroids in LC-ESI-MS for doping control analysis.

BACKGROUND: Two-step derivatization procedures were developed for the enhancement of the positive ESI in LC-MS detection of anabolic androgenic steroids, a class of prohibited substances with limited ionization efficiency in atmospheric pressure interfaces. The developed procedures are based on the esterification of hydroxyl groups of anabolic steroids with picolinic acid, followed by conversion of carbonyl groups to Schiff bases by either Girard's reagent T or 2-hydrazino pyridin. RESULTS: Ionization efficiency for the model derivatized compounds 19-norandrosterone (nandrolone main metabolite) and methasterone was higher by almost two orders of magnitude compared with the respective efficiency of the underivatized compounds. CONCLUSION: The obtained derivatives provided a significant improvement in the ESI sensitivity, compared with those of underivatized molecules in positive LC-ESI-ion trap-MS full-scan mode.

Distribution of organotin compounds in the bivalves of the Aegean Sea, Greece.

Five bivalve species--Mytilus galloprovinciallis (Mediterranean mussels), Venus gallina (stripped venus), Modiola barbatus L. (bearded horse mussels), Pecten jacobeus (scallops) and Callista chione (hard clams)--were collected from seven areas in Aegean Sea, Greece, between August 2001 and January 2003 and analyzed for organotins (OTs). The concentrations (as geometric means) found were 17.1 ng g-1 for tributyltin (TBT), 18.8 ng g-1 for dibutytltin (DBT), 7.8 ng g-1 for monobutyltin (MBT) and 13.0 ng g-1 for triphenyltin (TPhT) (wet weight), which are at similar or lower levels than those reported worldwide. Studying OTs distribution between different bivalve species, lower concentrations were observed in mediterranean mussels, possibly due to their growth in water column (grown on sea net pens in mussel farms), in contrast to the free-ranging species, collected from fishing grounds. Concentrations of the OTs in the examined bivalves varied seasonally.

Comparative study of pretreatment methods for the determination of metals in atmospheric aerosol by electrothermal atomic absorption spectrometry.

A comparative study of pretreatment methods for the determination of 10 elements (As, Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) in atmospheric aerosols by electrothermal atomic absorption spectrometry (ETAAS) was conducted. For the digestion of the particulates collected in filters, six methods were compared using a mixture of HNO(3) and HF with or without the addition of various oxidative agents (HClO(4) or H(2)O(2)) or acids (HCl). The comparative study was performed using loaded cellulose filter samples, which were digested in Parr bombs and heated in a conventional oven at 170 degrees C for 5h. The extraction efficiency and blanks were compared and it was proved that the digestion method using only HNO(3)-HF extracted most of the metals and gave the lowest blanks. The HNO(3)-HF mixture was selected for the development of an improved microwave digestion method specific for aerosol-loaded filters. The operating parameters were optimized, so that quantitative recovery of the reference materials NIST 1649a urban dust and NIST 1648 urban particulate matter was achieved. The blank of cellulose and teflon filters were also determined and compared. Teflon filters present the lowest blanks for all the elements. The obtained limits of detection for each type of filters were adequate for environmental monitoring purposes. ETAAS instrumental operation was also optimized for the compensation and the elimination of interferences. The temperature optimization was performed for each metal in every type of filter and optimized parameters are proposed for 10 elements.

Toxicity of organotin compounds to activated sludge.

Inhibition of respiration rate of activated sludge heterotrophic microorganisms was determined for tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), and triphenyltin (TPhT). TBT, DBT, and TPhT exhibit similar acute toxicity to activated sludge, while MBT is less toxic. The effect of various experimental parameters, such as sludge age, concentrations of suspended solids, and exposure time, on toxicity was investigated. An increase in sludge age or in the concentration of suspended solids reduces the observed inibition. Longer exposure seems to increase the inhibition of TBT, DBT, and TPhT during the first hours of exposure, while later the inhibition remains constant. In the case of MBT, 24 h after exposure, the respiration rate was similar to that of the control biomass.