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The monitoring of contaminants in fish species is pivotal for fishes' health and reproduction, as well as for human health. In the specific work, three major categories of contaminants, pesticides, pharmaceuticals, and macro and trace elements, were investigated in two major fish species, Dicentrarchus labrax and Solea solea, collected from Thermaikos Gulf, in Greece. To achieve this goal, three analytical methods using LC-MS/MS, GC-MS/MS, and ICP-MS were developed, validated, and applied to the collected fish samples. The results indicated a very low prevalence of caffeine and acetaminophen, both not exceeding 3.8 μg/kg fish. Similarly, thiabendazole, cypermethrin, and tricyclazole (pesticides) were found in a concentration range of 0.9 to 13.7 μg/kg fish, while in one D. labrax sample, traces of the metabolite of organochlorine pesticide DDT, o,p'-DDE were detected. Al, Mn, Fe, Zn, and Sr were the predominant trace elements in a concentration range of 500–20,000 μg/kg fish. Macro elements levels varied from 280 to 5405 mg/kg fish. Health risk assessment did not unveil an unacceptable risk for the human health of adults, apart from one sample presenting Hg above the regulatory levels. On the contrary, for children, the calculated hazard quotient values for Hg in all cases and for two As detections were higher than the threshold value of 1, indicating a potential risk. [ABSTRACT FROM AUTHOR]

Maternal milk is pivotal for infants' nutrition. It also portrays the chemical burden to which the mother has been exposed. One of the chemical families that is prevalent and related to potential toxic effects are volatile organic compounds (VOCs). In the present study, motivated by the scarcity of works dealing with concomitant VOC and metabolite determination in maternal milk, two new gas/liquid chromatography tandem mass spectrometry (GC-MS/MS, LC-MS/MS) methods for the simultaneous measurement of 25 VOCs and 9 of their metabolites, respectively, in maternal milk were developed and applied to 20 maternal milk samples collected from mothers in Greece. In parallel, a headspace solid-phase microextraction (HS-SPME)–GC-MS method was employed for the untargeted screening of chemicals. Low detection rates for benzene, toluene, styrene and p,m-xylenes, and three of their metabolites, namely N-acetyl-S-(benzyl)-L-cysteine (BMA, metabolite of toluene), 3-methylhippuric (3-MHA, metabolite of xylenes) and mandelic acid (MA as DL and R isomers, metabolites of styrene and ethylbenzene), were evidenced in concentrations varying from −1. HS-SPME–GC-MS disclosed the presence of common maternal milk constituents such as fatty acids. Nevertheless, bisphenol-A, bisphenol derivatives and phthalates were also detected. The infants' health risk assessment demonstrated a low risk and negligible carcinogenic risk, yet the detection of these compounds should not be underestimated. [ABSTRACT FROM AUTHOR]

Background: Bees encounter a plethora of environmental contaminants during nectar and pollen collection from plants. Consequently, after their entrance into the beehives, the transfer of numerous pollutants to apicultural products is inevitable. Methods: In this context, during the period of 2015–2020, 109 samples of honey, pollen, and beebread were sampled and analyzed for the determination of pesticides and their metabolites. More than 130 analytes were investigated in each sample by applying two validated multiresidue methods (HPLC-ESI-MS/MS and GC-MS/MS). Results: Until the end of 2020, 40 determinations were reported in honey, resulting in a 26% positive to at least one active substance. The concentrations of pesticides ranged from 1.3 ng/g to 785 ng/g honey. For seven active substances in honey and pollen, maximum residue limits (MRLs) exceedances were observed. Coumaphos, imidacloprid, acetamiprid, amitraz metabolites (DMF and DMPF), and tau-fluvalinate were the predominant compounds detected in honey, while several pyrethroids such as λ-cyhalothrin, cypermethrin, and cyfluthrin were also found. Pollen and beebread, as expected, accumulated a higher number of active substances and metabolites (32 in total), exhibiting almost double the number of detections. Conclusions: Although the above findings verify the occurrence of numerous pesticide and metabolite residues in both honey and pollen, the human risk assessment in the majority of the cases does not raise any concerns, and the same applies to bee risk assessment. [ABSTRACT FROM AUTHOR]

This study examines the occurrence of Polycyclic aromatic hydrocarbons (PAHs) in sediment samples collected from three areas (Saronikos Gulf, Piraeus harbor, Heraklion) across the Hellenic coastline, while PAHs distribution, sources and ecotoxicological risk are evaluated. According to the detected concentrations of PAHs, the most contaminated area was Piraeus (ΣPAHs: 125 to 2720 ng/g dw), followed by Saronikos Gulf (ΣPAHs: 21.4–1820 ng/g dw) and Heraklion (4.10–230 ng/g dw). Most sampling sites clearly show evidence for "combustion" in the source, whereas the data from Piraeus harbor indicate petroleum contamination as well. The calculated Toxic Equivalence Quotient (TEQ) and Mutagenic Equivalence Quotient (MEQ) values for Saronikos Gulf and Heraklion reveal low, or no, adverse health effects to exposed biota, while the pollution picture in Piraeus port indicates that BaP is the main contributor to carcinogenic and mutagenic risk. Risk assessment regarding dermal uptake of PAHs corroborated a negligible risk. • Polycyclic aromatic hydrocarbons (PAHs) were analysed is sediment samples from Greece. • Pireaus port (PIR) was the most contaminated area, followed by Saronikos Gulf (SG) and Heraklion (HER). • PAHs occurrence in most sampling sites is attributed to combustion sources. • Pireaus harbor suggest contamination both from combustion and petroleum sources. • The ecological risk assessment reveals that sediment from SG and HER pose a lower risk compared to the sediment of PIR. [ABSTRACT FROM AUTHOR]

Bee pollen contains a diversity of bioactive components. Nevertheless, since pollen is retrieved from a variety of plants, including the cultivated ones which are subjected to agrochemical treatments, its contamination is unavoidable. In this context, 45 samples of pollen were analysed with optimized analytical methods for trace and macro elements (ICP-MS), pesticides and metabolites residues (LC & GC-MS/MS) content. According to the results, potassium and iron were the most abundant in terms of concentration and frequency of detection, while the contribution of the most hazardous elements, such as lead, arsenic, cadmium and mercury, to the total concentration of trace elements was lower than 1%. For pesticides, coumaphos was the most frequently detected in the examined samples (22%), followed by propargite, azoxystrobin, dimethoate and cypermethrin. Non-carcinogenic health risk assessment demonstrated in the majority of cases negligible risk for adults and children. On the contrary, carcinogenic risk assessment considering a worst case scenario disclosed nickel and in less extent chromium and arsenic, as risk drivers, exhibiting in several samples carcinogenic risk values for adults above the safety threshold. Yet, regarding that both adults and children unlikely will daily consume such pollen quantities, especially on a long-term basis, an overestimation of risk should be appraised. • An optimized ICP-MS method for the analysis of 29 elements in pollen was applied. • LC-GC-MS/MS multiresidue methods unveiled pesticides' levels of 0.8–35 μg/kg. • Most hazardous elements contributed <1% to overall trace elements concentration. • Non-carcinogenic risk assessment showed negligible risk for adults and children. • Nickel, chromium and arsenic emerged as risk drivers in carcinogenic risk assessment. [ABSTRACT FROM AUTHOR]

A simple and effective analytical procedure has been developed for the determination of dimethoate (DIM) residues and its metabolite, omethoate, in serum samples of pesticide operators. For the selection of the most appropriate method for sample treatment, techniques such as headspace solid phase micro extraction and solid phase extraction and liquid-liquid extraction were applied. The applied method was based on toluene (2 mL) extraction of a 0.5 mL serum sample. In this report, it was observed that DIM concentration level affected the ratio of the area response of DIM and one of its oxygenated metabolite, omethoate. In this context, higher concentrations favoured the predominance of DIM while lower concentrations lead to the formation of omethoate. The method was validated using human serum samples spiked with DIM. Good linearity was obtained in the range of 1-10 ng/mL co-calculating DIM and omethoate. Various concentrations of DIM were mixed with serum and stored up to five days at -20°C. Recoveries ranged from 72% to 88% at two spiking levels for six replicates. The detection and quantification limit were calculated at 0.12 and 0.36 ng/mL of serum, respectively. Finally the comparison with the Acceptable Operator Exposure Level (AOEL) of DIM revealed that the maximum exposure of the operators reached the 30% of the AOEL for only two cases. [ABSTRACT FROM AUTHOR]

Soil constitutes a central environmental compartment that, due to natural and anthropogenic activities, is a recipient of several contaminants. Among them, organochlorine pesticides are of major concern, even though they have been banned decades ago in the European Union, due to their persistence and the health effects they can elicit. In the presented work, a gas chromatographic tandem mass spectrometric (GC-MS/MS) developed method was applied to soil samples after the suspected and potential use of formulations containing organochlorine active substance. One soil sample was positive to dieldrin at 0.018 mg kg−1. Predicted environmental concentration in soil (PECsoil) considering a single application of this active substance potentially attributed the finding in its past use. The subsequent health risk assessment showed negligible non-carcinogenic risk and tolerable carcinogenic risk. The latter signifies that repetitive and prolonged sampling can unveil the pragmatic projection of persistent chemicals' residues in the soil. [ABSTRACT FROM AUTHOR]