Assessment of organohalogenated pollutants in breast milk from the Czech Republic.

This biomonitoring survey brings new information on the occurrence of a total of 94 organohalogenated pollutants in 231 human breast milk samples collected in 2019 and 2021 from women living in two regions of the Czech Republic (Karvina and Ceske Budejovice). This study aimed to evaluate the concentrations of 6 indicator polychlorinated biphenyls (PCBs), 10 organochlorine pesticides (OCPs), 34 halogenated flame retardants (HFRs), 29 perfluoroalkyl and polyfluoroalkyl substances (PFAS) and 15 polychlorinated naphthalenes (PCNs). PCBs, OCPs, most of HFRs and PCNs were identified/quantified by gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)), while PFAS, hexabromocyclododecane isomers (HBCD), brominated phenols, and tetrabromobisphenol A (TBBPA) by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The mean value of the sum of the 6 indicator PCBs was 123.12 nanogram per gram of lipid weight (ng g-1 lw). Hexachlorobenzene (HCB), ß-hexachlorocyclohexane (ß-HCH) and p,p'-dichlorodiphenyl-dichloroethylene (p,p'-DDE) were the most abundant OCPs, detected in 100 % (mean 11.8 ng g-1 lw), 94.8 % (mean 6.1 ng g-1 lw) and 100 % (mean 101.5 ng g-1 lw) of samples, respectively. PCN congeners 20, 52 and 66 were detected in <1 % of the samples. The HFRs concentrations were relatively low compared to the levels of OCP; The detection rate of polybrominated diphenyl ethers (PBDEs, # 47, 99 and 153) ranged 21-68 % with a mean concentrations of 0.34 ng g-1 lw - 0.42 ng g-1 lw. PFAS concentrations were also low, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) dominant in this group (means of 22 pg ml-1 and 21 pg ml-1, respectively). Our results confirmed the long-term trend of declining levels of banned POPs in Czech mothers. The amounts of PCBs and OCPs were higher in older breastfeeding primiparous women.

Biomonitoring of 89 POPs in blood serum samples of Czech city policemen.

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.

Short- and medium-chain chlorinated paraffins in human blood serum of Czech population.

Short- and medium-chain chlorinated paraffins (SCCPs; MCCPs) are widespread environmental pollutants with bioaccumulation potential and adverse effects on human health. The analysis of blood serum is an important strategy to assess the human exposure to various contaminants, including SCCPs and MCCPs. Lately, the information about the exposure of Chinese population has been reported; nevertheless, data on human exposure to SCCPs and MCCPs outside East Asia are still very limited. In this pilot study, SCCPs and MCCPs were determined in 27 serum samples obtained from Czech adults. The samples were extracted by a three-step extraction (repeated with a clean solvent) by a mixture of n-hexane:diethyl ether (9:1, v/v) with subsequent clean-up on Florisil® solid phase extraction column. Gas chromatography coupled with high resolution mass spectrometry operated in negative chemical ionisation was employed for the instrumental analysis. The method recoveries ranged from 71 to 89% with repeatabilities of <20% (expressed as relative standard deviation). In the samples, SCCP concentrations were in the range of <150-2600 ng/g lipid weight, lw (median 370 ng/g lw) and the MCCP concentrations were in the range of <200-2110 ng/g lw (median 360 ng/g lw), respectively. To the best of our knowledge, our reported results are the first data about chlorinated paraffins in human blood serum in Europe, showing exposure to these compounds with yet to be studied effects on human health.

Interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) for flame retardant analysis in biological matrices: Results from the HBM4EU project.

The European Human Biomonitoring Initiative (HBM4EU) is coordinating and advancing human biomonitoring (HBM). For this purpose, a network of laboratories delivering reliable analytical data on human exposure is fundamental. The analytical comparability and accuracy of laboratories analysing flame retardants (FRs) in serum and urine were investigated by a quality assurance/quality control (QA/QC) scheme comprising interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds performed from 2018 to 2020 for the determination of ten halogenated flame retardants (HFRs) represented by three congeners of polybrominated diphenyl ethers (BDE-47, BDE-153 and BDE-209), two isomers of hexabromocyclododecane (α-HBCD and γ-HBCD), two dechloranes (anti-DP and syn-DP), tetrabromobisphenol A (TBBPA), decabromodiphenylethane (DBDPE), and 2,4,6-tribromophenol (2,4,6-TBP) in serum, and four metabolites of organophosphorus flame retardants (OPFRs) in urine, at two concentration levels. The number of satisfactory results reported by laboratories increased during the four rounds. In the case of HFRs, the scope of the participating laboratories varied substantially (from two to ten) and in most cases did not cover the entire target spectrum of chemicals. The highest participation rate was reached for BDE-47 and BDE-153. The majority of participants achieved more than 70% satisfactory results for these two compounds over all rounds. For other HFRs, the percentage of successful laboratories varied from 44 to 100%. The evaluation of TBBPA, DBDPE, and 2,4,6-TBP was not possible because the number of participating laboratories was too small. Only seven laboratories participated in the ICI/EQUAS scheme for OPFR metabolites and five of them were successful for at least two biomarkers. Nevertheless, the evaluation of laboratory performance using Z-scores in the first three rounds required an alternative approach compared to HFRs because of the small number of participants and the high variability of experts' results. The obtained results within the ICI/EQUAS programme showed a significant core network of comparable European laboratories for HBM of BDE-47, BDE-153, BDE-209, α-HBCD, γ-HBCD, anti-DP, and syn-DP. On the other hand, the data revealed a critically low analytical capacity in Europe for HBM of TBBPA, DBDPE, and 2,4,6-TBP as well as for the OPFR biomarkers.

Estimation of human exposure to polycyclic aromatic hydrocarbons (PAHs) based on the dietary and outdoor atmospheric monitoring in the Czech Republic.

In everyday life, humans can be exposed to various chemicals including ubiquitous polycyclic aromatic hydrocarbons (PAHs) mostly through food consumption and/or inhalation. In the presented study, we evaluated PAH concentrations in duplicate samples (n = 251). Concurrently, the outdoor concentrations of PM2.5-bound PAHs in filters (n = 179) were also monitored. The daily exposure to PAHs was subsequently estimated for the risk group of pregnant women living in two different cities (Most city and Ceske Budejovice city) in the Czech Republic. This is the first unique study in Europe to evaluate human daily exposure to 20 PAHs both from inhalation (outdoor air) and dietary intake. For the analysis of samples collected during the years 2016/2017, a gas chromatography coupled to tandem mass spectrometry was applied. Focusing on the diet samples, a slightly higher sum of detected PAHs was measured in duplicates obtained from the mothers living in the Most city (0.115-186 ng g-1) compared to the Ceske Budejovice city (0.115-97.1 ng g-1). This could be due to a higher occurrence of major analytes (pyrene, phenanthrene and fluoranthene) and the different composition of daily diet. The values of toxic and most often detected substance, namely benzo[a]pyrene (BaP), were also higher by 35% in the Most city. Regarding the outdoor air contamination (only particulate phase - PM2.5 was assessed), here the opposite situation was observed, relatively higher amounts of all PAHs were monitored in the Ceske Budejovice city (median: 2.22 ng m-3) than in the Most city (median: 1.07 ng m-3). These higher PAH concentrations in the Ceske Budejovice city are probably caused by more intense traffic, higher population and also by the occurrence of old-fashioned heating plant. Depending on a seasonal variability, especially during the cold season, the concentrations of BaP exceeded the European average emission limit (1 ng m-3) by 1.5-6 times. This highest inhalation exposure to all PAHs was observed in February. However, the dietary intake still represents the dominant contributor (>90%) to the total PAH exposure.