Guidance Document on Measurement Uncertainty for Laboratories performing PCDD/F and PCB analysis using Isotope Dilution Mass Spectrometry

This document on measurement uncertainty was developed within the network of the European Union Reference Laboratory (EURL) for Dioxins and PCBs in Feed and Food and the respective National Reference Laboratories (NRLs) of member states. Detailed guidance is given on the evaluation of measurement uncertainty in the quantitative analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs), to assist laboratories performing official feed and food control within the European Union, especially National Reference Laboratories (NRLs) and Official Laboratories (OFLs). It provides useful key elements contributing to further harmonization of compliance assessment and outlines practical aspects related to measurement uncertainty estimation. A new concept placing special emphasis on the inclusion of current method performance data is presented. The concept covers the full analytical process from sample receipt at the laboratory through sample storage, preparation and analysis, to data processing and reporting. In particular, it focuses on the role of analytical variability generally known as "measurement uncertainty" (MU) in the interpretation of analytical results for assessment of their compliance with a specification. Effects from sampling [EURACHEM/CITAC 2007, /18/] and transport also contributing to MU are acknowledged but not treated within the scope of this document. Two selected approaches for measurement uncertainty estimation are proposed for the determination of PCDD/Fs and PCBs in food and feed by gas chromatography-mass spectrometry (GC-MS) using internal standard stable isotope labelled analogues. An empirical, or “top-down”, approach combines contributions from intermediate (intra-laboratory) precision and trueness (expressed as bias) to estimate measurement uncertainty, both for individual congeners and for sum parameters. The working group recommends the use of the empirical approach as described in this document as the main option for MU estimation, because it is designed and developed to cover the whole analytical process and also includes the opportunity to reassess or update MU on a regular basis. However, an alternative methodology based on a semi-empirical approach following the EURACHEM/CITAC guide [EURACHEM/CITAC 2012, /12/] is also presented. It has been designed for laboratories new to this type of analysis that have generated data from initial validation studies. In this case the semi-empirical approach may be a good starting point, however the authors recommend implementing the empirical or top-down approach once enough data have been gathered.Working group fo Measurement Uncertainty in PCDD/F and PCB analysi

The effects of river flooding on dioxin and PCBs in beef

In 2008-2010, samples of meat from 40 beef cattle, along with grass, soil and commercial feed, taken from ten matched pairs of flood-prone and control farms, were analysed for PCDD/Fs and PCBs. Concentrations were higher in soil and grass from flood-prone farms. The beef samples from flood-prone farms had total TEQ levels about 20% higher than on control farms. A majority of flood-prone farms (7/10) had higher median levels in beef than on the corresponding control farm. This first controlled investigation into PCDD/F and PCB contamination in beef produced on flood-prone land, presents robust evidence that flooding is a contaminant transfer mechanism to cattle raised on river catchments with a history of urbanisation and industrialisation. PCDD/F and PCB sources in these river systems are likely to be a result of the legacy of contamination from previous industrialisation, as well as more recent combustion activity or pollution events. Crow

A retrospective investigation into the occurrence and human exposure to polychlorinated naphthalenes (PCNs), dibenzo-p-dioxins and furans (PCDD/Fs) and PCBs through cod liver products (1972–2017)

A retrospective analysis of a number of historical medicinal grade cod-liver oil samples produced in Northern Europe revealed relatively high contamination levels of PCNs, PCDD/Fs and PCBs. The total toxic equivalence (TEQ) associated with PCDD/Fs, dl-PCBs and PCNs was in the range 95 to 427 pg g-1 for Baltic cod-liver oils and from 70 to 148 pg g-1 for oils sourced from the North Atlantic. The corresponding range for canned cod liver products (Baltic Sea) sampled in 2017 ranged from 52 to 104 pg g-1 fat (33 to 34 pg g-1 ww). The contribution from PCBs to the overall TEQ toxicity was around 3 to 6-fold higher than from PCDD/Fs and ranged from 24 to 318 pg TEQ g-1ww. The estimated summed TEQ intakes of PCDD/Fs, dl-PCBs and dl-PCNs resulting from the consumption of the daily recommended doses was highest for the Baltic cod-liver oils ranging from 16 to 293 pg kg-1 body mass (bm) day-1 for an adult, 20 to 183 pg kg-1 bm day-1 for a teenager and 15 to 131 pg kg-1 bm day-1 for a child. The contribution to daily adult TEQ intake from PCNs alone, although relatively small is estimated to contribute up to 5-fold above the recent EFSA proposed TWI of 2 pg kg-1 bm. The results indicate that although currently produced fish oils may undergo rigorous purification procedures and show low contaminant levels, cod livers sourced from the Baltic and consumed locally, continue to contribute substantially to the dietary intake of these contaminants

PBDEs in cod (Gadus morhua) liver products (1972 to 2017): Occurrence and human exposure

PBDEs occur in a range of commonly consumed foods but there is very little current information on occurrence in dietary supplements such as cod liver oil or cod livers used as food. This study retrospectively investigated a number of these products, sourced from the Baltic Sea and North Atlantic, historically dating from 1972 to 2017. For the sum of 17 measured PBDEs (ΣPBDE), the concentrations ranged from 9.9 to 415 ng g-1 for the oils and from 10.5 to 13 ng g-1 for canned liver products. Concentrations in the oils were highest during the period from 1993 to 2001. For all samples, BDE-47 was the dominant congener with a maximum detected concentration of 308 ng g-1 in a Baltic cod liver oil from 1993. Human exposure to PBDEs from recommended doses were estimated for adults, teenagers and children. Depending on the age group, BDE-47 intakes ranged from 1.3 to 211.5 ng kg-1 bm day-1 (Baltic Sea), 2.9 to 12.7 ng kg-1 bm day-1 (Atlantic, Norway) and 1.1 to 4.8 ng kg-1 bm day-1 (Atlantic, Iceland). Intakes for the other dominant congeners, BDE-49, BDE-99 and BDE-100, were relatively low. The intake estimates of ΣPBDE were highest for Baltic cod liver oils ranging from 2.2 to 284.8 ng kg-1 bm day-1 for adults, 2.8 to 178 ng kg-1 bm day-1 for teenagers and 2.0 to 127.8 ng kg-1 bm day-1 for a child. Estimated weekly intake of ΣPBDE from canned cod liver was highest for adults, ranging from 17.6 to 25.1 ng kg-1 bm

Compositional profiles, persistency and toxicity of polychlorinated naphthalene (PCN) congeners in edible cod liver products from 1972 to 2017

Edible cod liver products including cod liver oil and canned cod liver, sampled over the last five decades from the North Atlantic region, including the Baltic Sea were analysed for a set of persistent and toxicologically significant polychlorinated naphthalene (PCN) congeners with some of the highest relative potencies (dioxin-like toxicity) among PCNs. The targeted congeners showed a near-universality of occurrence in all samples apart from the most recent sample of cod liver oil which was assumed to be highly purified, as cod livers from the same period and location showed appreciable amounts of PCNs. The majority of dominant congeners in legacy technical PCN mixtures were absent or occurred in low concentrations, raising the possibility that congeners arising from combustion related sources may be acquiring a greater significance following the decline and elimination of PCN production. The apparent appreciation in the relative amounts of PCN#70 in the last three to four decades may provide support for this view. The PCN contribution to dioxin-like toxic equivalence (TEQ) that was estimated for these samples (range 1.2–15.9 pg TEQ g −1) was significant in comparison to the EU regulated value of 1.75 pg TEQ g −1 for dioxins in fish oils. Most of the TEQ was associated with PCNs 66/67, 64/68, 69 and 73. Although metabolic processes are likely to influence this distribution, the profile is a little different to that observed in the tissues of higher order animals where PCNs #66/67 and #73 may contribute approximately 90% to the summed TEQ. The PCN contribution to dioxin-like toxic equivalence (TEQ) that was estimated for cod liver products (range 1.2–15.9 pg TEQ g −1) was significant in comparison to the EU regulated value of 1.75 pg TEQ g-1 for dioxins in fish oils. Most of the TEQ was associated with PCNs 66/67, 64/68, 69 and 73

Polybrominated dibenzo-p-dioxins and furans (PBDD/Fs): Contamination in food, humans and dietary exposure

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) have been recognised as environmental pollutants for decades but their occurrence in food has only recently been reported. They elicit the same type of toxic response as analogous polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with similar potencies and effects, and share similar origins - inadvertent production during combustion and occurrence as by-products in industrial chemicals. Surprisingly, PBDD/Fs have received considerably less attention than PCDD/Fs, perhaps because determination requires a higher degree of analytical competence, a result of the higher adsorptivity and lability associated with carbon-bromine bonding. For most populations, the principal exposure pathway is dietary intake. The PBDD/F toxicity arising from occurrence in foods has often been expressed as toxic equivalents (TEQs) using the same scheme developed for PCDD/Fs. This approach is convenient, but resulting TEQ estimates are more uncertain, given the known differences in response for some analogous congeners and also the different patterns of PBDD/F occurrence confirmed by the newer data. Further studies to consolidate potency factors would help to refine TEQ estimates. Characteristically, most foods and human tissues show more frequent and higher PBDF concentrations relative to PBDDs, reflecting major source patterns. Occurrence in food ranges from < 0.01 to several thousand pg/g (or up to 0.3 pg TEQ/g whole weight) which is comparable to PCDD/F occurrence (ΣPBDD/F TEQs are underestimated as not all relevant congeners are included). Plant based foods show higher PBDD/F: PCDD/F TEQ ratios. Reported PBDD/F dietary intakes suggest that some population groups, particularly young children, may exceed the revised tolerable weekly intake for dioxin-like contaminants (2 pg TEQ/kg bw/week), even for mean consumption estimated with lower bound data. It is evident that the omission of PBDD/Fs from the TEQ scheme results in a significant underestimation of the cumulative toxicity and associated risk arising from this mode of action

Dioxin-like polybrominated biphenyls (PBBs) and ortho-substituted PBBs in edible cod (Gadus morhua) liver oils and canned cod liverss

This study investigates the occurrence of polybrominated biphenyls (PBBs), a legacy flame retardant, in fishery products such as medicinal grade cod liver oils and canned liver products, sourced from the North Atlantic during 1972–2017. It also assesses the dietary and supplementary (the oils were commonly administered as dietary supplements to children and youth) intake of PBBs from these products. Summed ortho-PBB concentrations ranged from 770 to 1400 pg g−1 fat in the oils and from 99 to 240 pg g−1 whole weight in canned livers, with PBB-49, 52, 101 and 153 accounting for most of these levels. Among the more toxic non-ortho-PBBs, PBB-126 and PBB-169 were not detected, but PBB-77 concentrations ranged from 0.6 to 5.78 pg g−1 fat in the oils and 0.06–0.126 pg g−1 whole weight in canned livers. During 1972–1993, PBB contamination levels were similar for cod liver oils from the Baltic Sea and other North Atlantic regions, but over the timescale of the study, Baltic Sea products appear to show a decline in PBB concentrations. As PBB-77 was the only dioxin-like PBB detected in the samples, the corresponding supplementary (oils, 1972–2001) and dietary (cod liver from 2017) intakes were very low, at < 0.001 pg TEQ kg−1 bm d−1 (or < 0.01 pg TEQ kg−1 bm d−1 upper bound) for the sum of all the measured dioxin-like PBBs –four to six orders of magnitude lower than that arising from other dioxin-like contaminants that were shown to occur in these products, from earlier studies

137Caesium, 40Potassium and potassium in raw and deep-oil stir-fried mushroom meals from Yunnan in China

A number of wild, edible mushroom species (Baorangia bicolor, Boletus calopus, Boletus obsclereumbrinus, Butyriboletus roseoflavus, Rubroboletus sinicus, Rugiboletus extremiorientalis and Xerocomus sp.) were collected in 2017, from Yunnan (Yuxi prefecture) in SW China. Samples of raw and stir-fried pools of these specimens were analysed for radioisotopes 137Cs (caesium) and 40 K (potassium), and for total K concentrations. On a whole (wet) weight (ww) basis, 137Cs activity ranged from <0.10 to 0.75 Bq kg−1 for raw, and from 0.5 to 4.4 Bq kg-1 in stir-fried mushrooms. Radiopotassium (40K) activity ranged from 57 to 96 Bq kg−1 ww for raw, and 170 to 370 Bq kg−1 ww for stir-fried mushrooms, while the corresponding concentration ranges for total K were 2100–3400 mg kg−1 ww (mean: 2800 ± 3900 mg kg−1 ww), and 6000–13000 mg kg−1 ww) mean: 8700 ± 2100 mg kg−1 ww), respectively. This data indicates that mushrooms from this region show negligible 137Cs contamination with evidently higher activity levels of 40K. The deep oil stir-frying process results in enrichment in the resulting meals for all three determinants. 100 g meal portions showed 137Cs activity in the range <0.08 to 0.44 Bq 100 g−1 ww (mean 0.15 ± 0.12 Bq 100 g−1 ww), and 40K activity from 16 to 37 Bq 100 g−1 ww (mean 24 ± 6 Bq 100 g−1 ww). The consequent exposure from 40K contained in a single 100 g serving and weekly (100 g x7) servings was equivalent to radiation doses in the range of 0.099 to 0.23 µSv and 0.68–1.6 µSv per capita (means 0.15 ± 0.04 and 1.1 ± 0.3 µSv). This is equivalent to doses in the range of 0.0017 to 0.0038 µSv kg-1 bm day-1 and 0.011 to 0.027 µSv kg-1 bm week-1 respectively (mean values of 0.0025 ± 0.006 µSv kg-1 bm day-1and 0.018 ± 0.004 µSv kg-1 bm week-1). Analogically to the annual 137Cs radiation exposure resulting from high rates of annual consumption (20–24 kg per capita), the estimated annual dose of radiation from 40K would range from 0.34 up to 0.92 µSv kg-1 bm (mean 0.60 µSv kg-1 bm). Thus in practice, high annual consumption rates of wild, stir-fried mushrooms as seen in Yunnan, would result in negligible internal doses from decay of artificial 137Cs, relative to that from natural 40K. The 100 g servings also contained between 590–1300 mg K making this local food one of the top dietary sources of nutritionally important potassium for local consumers