In this biomonitoring study, we evaluated the concentrations of 8 polychlorinated biphenyls (PCBs), 11 organochlorinated pesticides (OCPs), 33 brominated flame retardants (BFRs), 7 novel brominated and chlorinated flame retardants (novel FRs) and 30 per- and polyfluoroalkylated substances (PFAS) in human serum samples (n = 274). A total of 89 persistent organic pollutants (POPs) were measured in blood serum samples of city policemen living in three large cities and their adjacent areas (Ostrava, Prague, and Ceske Budejovice) in the Czech Republic. All samples were collected during the year 2019 in two sampling periods (spring and autumn). The identification/quantification of PCBs, OCPs, BFRs, novel FRs and PFAS was performed by means of gas chromatography coupled to (tandem) mass spectrometry (GC-MS/(MS)) and ultra-high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-MS/MS). The most frequently detected pollutants were perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), 2,2',3,4,4',5'-hexachlorobiphenyl (CB 138), 2,2',4,4',5,5'-hexachlorobiphenyl (CB 153), 2,2',3,3',4,4',5-heptachlorobiphenyl (CB 170), 2,2',3,4,4',5,5'-heptachlorobiphenyl (CB 180), hexachlorobenzene (HCB), and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) quantified in 100% of serum samples. In the serum samples, the concentrations of determined POPs were in the range of 0.108-900 ng g^-1 lipid weight (lw) for PCBs, 0.106-1016 ng g^-1 lw for OCPs, <0.1-618 ng g^-1 lw for FRs and <0.01-18.3 ng mL^-1 for PFAS, respectively. Locality, sampling season, and age were significantly associated with several POP concentrations. One of the important conclusions was that within the spring sampling period, statistically significant higher concentrations of CB 170 and CB 180 were observed in the samples from Ostrava (industrial area) compared to Prague and Ceske Budejovice. Older policemen had higher concentrations of five PCBs and two OCPs in blood serum.

Human biomonitoring (HBM) of cadmium is essential to assess and prevent toxic exposure. Generally, low cadmium levels in urine and blood of the general population place particularly high demands on quality assurance and control measures (QA/QC) for cadmium determination. One of the aims of the HBM4EU project is to harmonize and advance HBM in Europe. Cadmium is one of the chemicals selected as a priority substance for HBM implementation in the 30 European countries under HBM4EU. For this purpose, analytical comparability and accuracy of the analytical laboratories of participating countries was investigated in a QA/QC programme comprising interlaboratory comparison investigations (ICI) and external quality assurance schemes (EQUAS). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds for the determination of cadmium in urine and blood. The majority of the 43 participating laboratories achieved satisfactory results, although low limits of quantification were required to quantify Cd concentrations at general population exposure levels. The relative standard deviation of the participants' results obtained from all ICI and EQUAS runs ranged from 8 to 36% for cadmium in urine and 8-28% for cadmium in blood. Applying inductively-coupled plasma mass spectrometry (ICP-MS), using an internal standard, and eliminating molybdenum oxide interferences was favourable for the accurate determination of cadmium in urine and blood. Furthermore, the analysis of cadmium in urine was found to have a critical point at approximately 0.05 μg/l, below which variability increased and laboratory proficiency decreased. This QA/QC programme succeeded in establishing a network of laboratories with high analytical comparability and accuracy for the analysis of cadmium across 20 European countries.

Interference of residual lipids is a very common problem in ultratrace analysis of contaminants in fatty matrices. Therefore, quick and effective clean-up techniques applicable to multiple groups of analytes are much needed. Cartridge and dispersive solid-phase extraction (SPE and dSPE) are often used for this purpose. In this context, we evaluated the lipid clean-up efficiency and performance of four commonly used sorbents—silica, C18, Z-Sep, and EMR-lipid—for the determination of organic pollutants in fatty fish samples (10%) extracted using ethyl acetate or the QuEChERS method. Namely, 17 polychlorinated biphenyls (PCBs), 22 organochlorine pesticides (OCPs), 13 brominated flame retardants (BFRs), 19 per- and polyfluoroalkyl substances (PFAS), and 16 polycyclic aromatic hydrocarbons (PAHs) were determined in this study. The clean-up efficiency was evaluated by direct analysis in real time coupled with time-of-flight mass spectrometry (DART-HRMS). The triacylglycerols (TAGs) content in the purified extracts were significantly reduced. The EMR-lipid sorbent was the most efficient of the dSPE sorbents used for the determination of POPs and PAHs in this study. The recoveries of the POPs and PAHs obtained by the validated QuEChERS method followed by the dSPE EMR-lipid sorbent ranged between 59 and 120%, with repeatabilities ranging between 2 and 23% and LOQs ranging between 0.02 and 1.50 µg·kg⁻¹.

The Human Biomonitoring for Europe initiative (HBM4EU) aims to study the exposure of citizens to chemicals and potentially associated health effects. One objective of this project has been to build a network of laboratories able to answer to the requirements of European human biomonitoring studies. Within the HBM4EU quality assurance and quality control scheme (QA/QC), a number of interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) were organized to ensure data consistency, comparability and reliability. Bisphenols are among the prioritized substance groups in HBM4EU, including bisphenol A (BPA), bisphenol S (BPS) and bisphenol F (BPF) in human urine. In four rounds of ICI/EQUAS, two target concentration levels were considered, related to around P25 and P95 of the typical exposure distribution observed in the European general population. Special attention was paid to the conjugated phase II metabolites known to be most dominant in samples of environmentally exposed individuals, through the analysis of both native samples and samples fortified with glucuronide forms. For the low level, the average percentage of satisfactory results across the four rounds was 83% for BPA, 71% for BPS and 62% for BPF. For the high level, the percentages of satisfactory results increased to 93% for BPA, 89% for BPS and 86% for BPF. 24 out of 32 participating laboratories (75%) were approved for the analyses of BPA in the HBM4EU project according to the defined criterion of Z-scores for both low and high concentration levels in at least two ICI/EQUAS rounds. For BPS and BPF, the number of qualified laboratories was 18 out of 27 (67%) and 13 out of 28 (46%), respectively. These results demonstrate a strong analytical capability for BPA and BPS in Europe, while improvements may be needed for BPF.