The migration of phthalates into foodstuffs from food-contact materials (FCM) is a well-known source of food contamination. In 2005, the European Food Safety Authority finalized its risk assessment for several of the classical phthalate plasticizers. In their risk management procedure the European Commission transformed the tolerable daily intakes established by the Authority into legislative limits for phthalates in both plastic and food simulants, while taking exposure from other sources into consideration. These limits have been into force since 1 July 2008. A detailed interpretation of the regulation of these substances was agreed upon in the European network of FCM reference laboratories. This paper reports results from a Danish control campaign of samples collected by official food inspectors and analysed by a newly validated analytical method run under accreditation. Samples were from FCM producers, FCM importers and importers of packed foodstuffs from third-party countries. Products containing phthalates above the current limits were found in several categories of FCM: conveyor belts (six of six), lids from packed foodstuffs in glasses (eight of 28), tubes for liquid foodstuffs (four of five) and gloves (five of 14). More than 20% of the samples analysed contained dibutylphthalate (DBP) or di-(2-ethylhexyl)phthalate (DEHP) above the compositional limits of 0.05% and 0.1%, respectively. Analysis of residual phthalates in metal lid gaskets instead of analysis of phthalates in the food when controlling foodstuffs packed outside the European Union proved to be an efficient and simple control method. All findings of phthalates were associated with the use of plasticized polyvinylchloride (PVC).
Due to large knowledge gaps in chemical composition and toxicological data for substances involved, paper and board food-contact materials (P&B FCM) have been emerging as a FCM type of particular concern for consumer safety. This study describes the development of a step-by-step strategy, including extraction, high-performance liquid chromatography (HPLC) fractionation, tentative identification of relevant substances and in vitro testing of selected tentatively identified substances. As a case study, we used two fractions from a recycled pizza box sample which exhibited aryl hydrocarbon receptor (AhR) activity. These fractions were analysed by gas chromatography (GC) and ultra-HPLC (UHPLC) coupled to quadrupole time-of-flight mass spectrometers (QTOF MS) in order tentatively to identify substances. The elemental composition was determined for peaks above a threshold, and compared with entries in a commercial mass spectral library for GC-MS (GC-EI-QTOF MS) analysis and an in-house built library of accurate masses for substances known to be used in P&B packaging for UHPLC-QTOF analysis. Of 75 tentatively identified substances, 15 were initially selected for further testing in vitro; however, only seven were commercially available and subsequently tested in vitro and quantified. Of these seven, the identities of three pigments found in printing inks were confirmed by UHPLC tandem mass spectrometry (QqQ MS/MS). Two pigments had entries in the database, meaning that a material relevant accurate mass database can provide a fast tentative identification. Pure standards of the seven tentatively identified substances were tested in vitro but could not explain a significant proportion of the AhR-response in the extract. Targeted analyses of dioxins and PCBs, both well-known AhR agonists, was performed. However, the dioxins could explain approximately 3% of the activity observed in the pizza box extract indicating that some very AhR active substance(s) still remain to be identified in recycled low quality P&B.
Application of QuEChERS as a new quick and easy method for screening of polycyclic aromatic hydrocarbons (PAHs) was developed, validated and used for quantification (GC-QTOF-MS) of 4 PAHs, namely benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene. A clean-up step using Zirconium based dispersive SPE was applied. Validation based on spiked samples (0.5, 1 and 4 µg/kg) revealed a limit of quantification (LOQ) for the 4 PAH compounds in the range of 0.14-0.24 μg/kg for fish and 0.12-0.24 μg/kg for raw barley. Overall recoveries ranged from 88 to 117% with repeatability and in-house reproducibility from 2.6 to 16%. The method was applied to 9 malt samples which were found to contain the sum of 4 PAH from <0.36 µg/kg for raw barley to 26 µg/kg for peat smoked barley. For 5 smoked fish samples the sum of PAH4 ranged from <0.34 µg/kg for cold smoked salmon to 2.2 µg/kg for hot smoked mackerel. In general it was found that the method could be used as a fast screening for evaluation of smoked fish according to EU Commission maximum concentrations of benzo[a]pyrene (2.0 µg/kg) and the sum of PAH4 (10 µg/kg).
Chronic eczematous hand dermatoses with and without contact allergies are complex diseases, which makes it a challenge to select the best treatment and obtain an optimal patient experience and a satisfactory treatment result. The aim of this study was to evaluate retrospectively the clinical effect and patient experience of local treatment with psoralen plus ultraviolet A (PUVA) soaks and TL01 phototherapy for severe chronic hand dermatoses, and also to evaluate the quality of life for the subgroup of patients with allergic contact dermatitis including Compositae allergy. A retrospective evaluation of results for 94 consecutive patients having received a total of 121 treatment courses with local PUVA soaks or TL01 phototherapy for one of the following diagnoses (n=number of treatment courses): psoriasis (n=19), hyperk-eratotic hand eczema (n=27), Pustulosis Palmoplantaris (PPP) (n=22), vesicular eczema (n=16), Compositae dermatitis (n=24), and allergic contact dermatitis (n=13). Moreover, semi-structured interviews with 6 selected patients having multiple contact allergies including Compositae allergy were used to evaluate quality of life. As a result, we found that PUVA soaks has good effect in patients with psoriasis and hyperkeratotic hand eczema and local phototherapy for chronic hand dermatoses is a useful treatment option in selected cases.
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