Analysis and Quality Control of WHO- and UNEP-Coordinated Human Milk Studies 2000–2019: Polybrominated Diphenyl Ethers, Hexabromocyclododecanes, Chlorinated Paraffins and Polychlorinated Naphthalenes

Abstract Four different analytical methods were used for the determination of (1) polybrominated diphenyl ethers (PBDE), (2) hexabromocyclododecanes (HBCDD), (3) chlorinated paraffins (CP) and (4) polychlorinated naphthalenes (PCN) in human milk samples of the WHO/UNEP-coordinated exposure studies. As a laboratory accredited according to EN ISO/IEC 17025, a comprehensive quality control program was applied to assure the reliability of results. This included procedural blanks, the use of numerous quality control samples as in-house reference materials and the participation in proficiency tests (PTs). Trueness was estimated from the PT samples using the assigned values. The mean absolute deviation of the sum parameters ∑PBDE 6 and ∑PBDE 7 from the assigned values of 53 PT samples analysed between 2006 and 2021 was 12% and 14%, respectively. For α-HBCDD as the most abundant diastereomer and the sum of α-, β- and γ-HBCDD, deviations of the reported value from the assigned value of the proficiency tests (31 samples, analysed between 2007 and 2021) were in most cases below 40% over a large concentration range, e.g., for α-HBCDD, between 0.0084 and 19 ng/g fw. For concentrations above 0.5 ng/g lipid, the deviation was in the range of approximately 0–30%. For short-chain and medium-chain CP (SCCP and MCCP) all z -scores achieved in interlaboratory comparisons during 2017–2020 were within ±2 z and therefore satisfactory (13 PT samples were analysed for ΣCP, ΣSCCP and ΣMCCP using the GC-ECNI-Orbitrap-HRMS method, eight results achieved for ΣCP using the GC-EI-MS/MS method). Due to the lack of available proficiency tests for PCN at the time of measuring the human milk samples of the 2016–2019 period, an external validation for control of the trueness was performed through an interlaboratory comparison with an independent laboratory. The deviation of the ΣPCN 13 in five test samples between the external laboratory and CVUA Freiburg was in the range from 3 to 20%. At a later stage (in 2021), the laboratory participated successfully in the first interlaboratory comparison study on PCN congeners in cod liver oil. The z -scores for seven congeners and two sum parameters were within ±2 z and therefore satisfactory. Also, the results for other of the altogether 26 PCN congeners were in accordance with the median values reported by all participants. As a result, the determination of PBDE, HBCDD, CP and PCN in human milk samples of the WHO/UNEP-coordinated exposure studies followed the strict rules of the accreditation system and the general criteria for the operation of testing laboratories as laid down in EN ISO/IEC 17025.