Evaluating the efficiency of the 2020 ban of BPA and BPS in thermal papers in Switzerland.

Thermal printing technology requires a color developer to activate the dye under the action of heat. Bisphenol A (BPA) has traditionally been used for this purpose, although it has increasingly been replaced by bisphenol S (BPS) in recent years. Due to concerns regarding their toxicity, the Swiss authorities have banned both BPA and BPS from thermal papers since 2020. The impact of this regulatory decision was evaluated during 3 monitoring campaigns: in 2013-2014, 2019 and 2021. They were used to describe the starting point, the transition phase, and the status after entry into force of the ban, respectively. Whereas the use of BPA as color developer dropped from 82.2% in 2013/14 to 10.8% in 2021, the fraction of BPS-based thermal paper rose from 3.1% to 19.1% during the same period, despite being banned. However, Pergafast® 201 (PF201) is now the main color developer in thermal paper in Switzerland, with an occurrence of 60.3%. Other alternatives such as D-8, TGSA, PPSMU, NKK-1304, BPS-MAE, D-90 and Blue4est® have only been marginally detected. This study demonstrates the efficiency of the regulatory measure and the feasibility to substitute BPA in thermal papers with less-toxic alternatives.

Pyrrolizidine Alkaloids: The Botanical Origin of Pollen Collected during the Flowering Period of Echium vulgare and the Stability of Pyrrolizidine Alkaloids in Bee Bread.

Previous studies have shown that pollen products sold as nutritional supplements and used in apitherapy may contain toxic pyrrolizidine alkaloids (PAs) if bees collect pollen from PA-containing plants, such as Echium vulgare. In this study, the botanical origin of pollen from two observation sites was studied. Despite a high PA content in pollen samples that bees collected during E. vulgare's flowering period, bees were found to collect relatively few Echium pollen loads. Thus, the monitoring of pollen loads collected at the apiaries is unviable to estimate the risk of PA contamination in pollen or bee bread. In a second step, the stability of PAs in bee bread samples containing PAs at concentrations of 2538 ng/g and 98 ng/g was assessed over a period of five or six months, respectively. No significant PA reduction was observed in bee bread stored at 15 °C, but there were overall PA reductions of 39% and 33% in bee bread stored at 30 °C, reflecting hive conditions. While PA N-oxides decreased over time, other types of PAs remained relatively stable. Monitoring PAs in pollen products remains important to ensure consumer safety and should include echivulgarine (and its N-oxide), the major PA type found in pollen from E. vulgare.

Endocrine activity of alternatives to BPA found in thermal paper in Switzerland.

Alternatives to bisphenol A (BPA) are more and more used in thermal paper receipts. To get an overview of the situation in Switzerland, 124 thermal paper receipts were collected and analyzed. Whereas BPA was detected in most samples (n=100), some alternatives, namely bisphenol S (BPS), Pergafast® 201 and D-8 have been found in 4, 11 and 9 samples respectively. As no or few data on their endocrine activity are available, these chemicals and bisphenol F (BPF) were tested in vitro using the H295R steroidogenesis assay. 17ß-Estradiol production was induced by BPA and BPF, whereas free testosterone production was inhibited by BPA and BPS. Both non-bisphenol substances did not show significant effects. The binding affinity to 16 proteins and the toxicological potential (TP) were further calculated in silico using VirtualToxLab™. TP values lay between 0.269 and 0.476 and the main target was the estrogen receptor ß (84.4 nM to 1.33 µM). A substitution of BPA by BPF and BPS should be thus considered with caution, since they exhibit almost a similar endocrine activity as BPA. D-8 and Pergafast® 201 could be alternatives to replace BPA, however further analyses are needed to better characterize their effects on the hormonal system.

Pyrrolizidine alkaloids in tea, herbal tea and iced tea beverages- survey and transfer rates.

The transfer rate of 37 pyrrolizidine alkaloids (PA) found in ten naturally contaminated teas and herbal teas to their brews was studied in detail. Mixed herbal, peppermint, red bush, senna, black tea and green tea infusions were prepared according to the ISO guide and vendor's instructions, respectively, and parameters like herb-to-water ratio, steeping time and multiple extractions studied. In general, a transfer rate of 38-100% (median 95%) for brews following vendor's instructions was determined. The total concentration range of PA in these ten samples was 154-2412 ng/g (median 422 ng/g) in the herb and for single analytes 0.1-170 ng/g. Seven of the 37 PA occurred unexpectedly; these were tentatively identified and quantified by liquid chromatography-high resolution mass spectrometry (LC-HR-MS), since their contributions to total PA-content matter. Additionally, 46 iced tea beverages were analysed for their PA-load, determined to be in the range 0-631 ng/L (median 40 ng/L). The applied solid-phase extraction (SPE) clean-up turned out to be capable of separating PA in the free base pyrrolizidine alkaloids (PAFB) and their N-oxides (PANO) in a two-step elution, which was a valuable tool to support identification of unexpected PA. Further, atropine was found in 50% of the ten tea herb samples (range: 1-4 ng/g) and in 13% of the iced tea beverage samples (range: 2-65 ng/L).

Chemical fingerprinting identifies Echium vulgare, Eupatorium cannabinum and Senecio spp. as plant species mainly responsible for pyrrolizidine alkaloids in bee-collected pollen.

Various studies have shown that bee-collected pollen sold as nutritional supplements may contain toxic pyrrolizidine alkaloids (PAs) and, thus, pose a potential health risk for consumers. The level of contamination may vary according to its geographical and botanical origin. Here, the PA content of pollen produced in Switzerland was studied and 32 commercially available bee-collected pollen supplements produced between 2010 and 2014 were analysed. In addition, at what time period bees collect PA-containing pollen was investigated. Hence, this study looked into the occurrence of PAs in pollen samples collected daily during two-to-three consecutive seasons. Furthermore, the PA spectrum in pollen was compared to the spectrum found in flower heads of PA-plants to unambiguously identify plants responsible for PA contamination of pollen. The PA concentration of commercial and daily collected pollen was determined by target analysis using an HPLC-MS/MS system, allowing the detection of 18 different PAs and PA N-oxides found in the genera Echium, Eupatorium and Senecio, while the comparison of the PA spectrum in pollen and flower heads was performed by LC-HR-MS, allowing the detection of all PA types in a sample, including saturated, non-carcinogenic PAs. Of the commercially available pollen, 31% contained PAs with a mean concentration of 319 ng/g, mainly Echium- and Eupatorium-type PAs, while the PA concentrations were below the limit of quantitation (LOQ) in 69% of the pollen samples. Bees collected pollen containing Echium-type PAs mainly in June and July, while they gathered pollen containing Eupatorium-type PAs from mid-July to August. Senecio-type PAs appeared from June to September. Comparison of the PA array in pollen and plants identified E. vulgare and E. cannabinum as the main plants responsible for PA contamination of Swiss bee-collected pollen, and to a lesser extent also identified plants belonging to the genus Senecio.

Quinolizidine alkaloids and phomopsins in lupin seeds and lupin containing food.

In recent years there has been growing interest in replacing (genetically modified) soya by lupin. Lupin seeds, flours and lupin containing food have been analyzed in order to assess the relevance of a potential health hazard given by mycotoxins and/or naturally occurring alkaloids. Since not all important alkaloids used for quantitation were commercially available, isolation of lupanine, 13alpha-hydroxylupanine and angustifoline from lupin flours of high alkaloid contents was performed. Alkaloids were analyzed by GC-MS/GC-FID in parallel, while the phomopsin mycotoxins were analyzed by ELISA, since chromatographic methods were not sensitive enough and required time-consuming sample cleanup. The analyzed lupin containing foods were free of phomopsins. In foods where lupin was only a minor constituent the alkaloid content was of no concern. However, roasted lupin beans intended as coffee surrogate had alkaloid contents close to the Australian intervention limit of 200 microg/g.

Natural occurrence of bisphenol F in mustard.

Bisphenol F (BPF) was found in mustard up to a concentration of around 8 mg kg(-1). Contamination of the raw products or caused by the packaging could be ruled out. Also, the fact that only the 4,4'-isomer of BPF was detected spoke against contamination from epoxy resin or other sources where technical BPF is used. Only mild mustard made of the seeds of Sinapis alba contained BPF. In all probability BPF is a reaction product from the breakdown of the glucosinolate glucosinalbin with 4-hydroxybenzyl alcohol as an important intermediate. Hot mustard made only from brown mustard seeds (Brassica juncea) or black mustard seeds (Brassica nigra) contained no BPF. BPF is structurally very similar to bisphenol A and has a similar weak estrogenic activity. The consumption of a portion of 20 g of mustard can lead to an intake of 100-200 µg of BPF. According to a preliminary risk assessment, the risk of BPF in mustard for the health of consumers is considered to be low, but available toxicological data are insufficient for a conclusive evaluation. It is a new and surprising finding that BPF is a natural food ingredient and that this is the main uptake route. This insight sheds new light on the risk linked to the family of bisphenols.