A review of Fourier Transform Infrared (FTIR) spectroscopy used in food adulteration and authenticity investigations.

The increasing demand for food and the globalisation of the supply chain have resulted in a rise in food fraud, and recent high profile cases, such as the Chinese milk scandal in 2008 and the EU horsemeat scandal in 2013 have emphasised the vulnerability of the food supply system to adulteration and authenticity frauds. Fourier Transform Infrared (FTIR) spectroscopy is routinely used in cases of suspected food fraud as it offers a rapid, easy and reliable detection method for these investigations. In this review, we first present a brief summary of the concepts of food adulteration and authenticity as well as a discussion of the current legislation regarding these crimes. Thereafter, we give an extensive overview of FTIR as an analytical technique and the different foods where FTIR analysis has been employed for food fraud investigations as well as the subsequent multivariate data analyses that have been applied successfully to investigate the case of adulteration or authenticity. Finally, we give a critical discussion of the applications and limitations of FTIR, either as a standalone technique or incorporated in a test battery, in the fight against food fraud.

Stability of Isocyanates Sampled in Fire Smokes.

Inhalation of airborne isocyanates is associated with acute asthma attacks and inflammation in the respiratory tract as well as cancer. These highly reactive compounds are used as monomers in various applications such as foams for insulation materials and upholstery furniture and are therefore commonly found in fire smoke from insulation materials, such as rigid polyisocyanurate (PIR) foams. Consequently, there is an increasing concern regarding the potential adverse health effects they may cause during this type of exposure.The aim of this study was to investigate the stability of generated isocyanates from aerobic pyrolysis of PIR after sampling in the derivatization solution as well as after sample preparation to establish the optimal storage conditions and rate of degradation. Both airborne and particle-bound isocyanates were collected, using dibutylamine as derivatization agent in a midget impinger and impregnated filter after the impinger. The rapid degradation of the generated isocyanates after sampling emphasizes the need for a prompt sample preparation and analysis, in particular for the collected mono-isocyanates, as the concentration decreased by 50% within 4-8 h.

An effect-directed strategy for characterizing emerging chemicals in food contact materials made from paper and board.

Food contact materials (FCM) are any type of item intended to come into contact with foods and thus represent a potential source for human exposure to chemicals. Regarding FCMs made of paper and board, information pertaining to their chemical constituents and the potential impacts on human health remains scarce, which hampers safety evaluation. We describe an effect-directed strategy to identify and characterize emerging chemicals in paper and board FCMs. Twenty FCMs were tested in eight reporter gene assays, including assays for the AR, ER, AhR, PPARγ, Nrf2 and p53, as well as mutagenicity. All FCMs exhibited activities in at least one assay. As proof-of-principle, FCM samples obtained from a sandwich wrapper and a pizza box were carried through a complete step-by-step multi-tiered approach. The pizza box exhibited ER activity, likely caused by the presence of bisphenol A, dibutyl phthalate, and benzylbutyl phthalate. The sandwich wrapper exhibited AR antagonism, likely caused by abietic acid and dehydroabietic acid. Migration studies confirmed that the active chemicals can transfer from FCMs to food simulants. In conclusion, we report an effect-directed strategy that can identify hazards posed by FCMs made from paper and board, including the identification of the chemical(s) responsible for the observed activity.

Non-targeted screening for contaminants in paper and board food-contact materials using effect-directed analysis and accurate mass spectrometry.

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.

Fractionation of extracts from paper and board food contact materials for in vitro screening of toxicity.

Paper and board used as food contact materials (FCMs) are chemically complex matrices, partly due to the naturally occurring substances in paper and board, but also due to the chemical treatment of the paper used to make it suitable for food contact. In order to assure the safety of packaging materials, information on the exposure as well as on the toxicity of substances in the packaging must be obtained. This study describes a comprehensive method for the extraction and fractionation of substances present in paper and board FCMs for further investigation by in vitro testing and chemical analysis. The extraction efficiency and the fractionation process were validated by determining recoveries in extracts from paper and board fortified with five surrogates of known concentration. The recoveries for the five surrogates were between 20% and 104% in the raw extract and between 21% and 109% after extraction and fractionation. The fractionation both reduces the number of compounds to be identified and works as a sample clean-up by reducing matrix effects. Raw extracts and fractions from two paper and board FCMs were furthermore tested in the aryl hydrocarbon receptor (AhR) reporter gene assay. Both raw extracts and two of the fractions of the raw extracts gave a positive response in the AhR assay. The strategy of extraction followed by fractionation offers a powerful tool in order to make the workflow for screening FCMs for potentially adverse effects more efficient.