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Vegetable fats and oils are prone to contamination by mineral oil hydrocarbons due to the lipophilic and ubiquitous character of the latter. As the aromatic fraction of these hydrocarbons, MOAH, is associated with carcinogenicity, mutagenicity, and detrimental effects on foetal development, finding strategies to limit or reduce their contamination is highly relevant. Deodorisation (i.e. a refining step) has shown the ability to remove MOAH < C25 in vegetable fats and oils, but there is little information about the structures removed. Therefore, the present study investigated the impact of deodorisation conditions on the removal of different structures of MOAH in spiked coconut oil. An inscribed central composite design was built with time and temperature as variables (0.5-4h, 150-240 °C), while pressure (3 mbar) and steam flow (1 g water/g oil per hour) were kept constant. The analysis of MOAH in the oil was performed using a fully automated liquid chromatography coupled with two parallel comprehensive two-dimensional gas chromatography systems with flame ionisation and time-of-flight mass spectrometric detection. Response surfaces plotting the MOAH loss according to time and temperature were built for different MOAH fractions. The latter were defined based on the number of aromatic rings (>3 or ≤3) and the number of carbon atoms present (C16-C20, C20-C24, C24-C35, C35-C40). It was found that at 200 °C, compounds < C24, including weakly alkylated triaromatics, could be reduced to below the limit of quantification, while at 230 °C, it was possible to remove >60% of the C24-C35 fraction, including pentaromatics of low alkylation. [ABSTRACT FROM AUTHOR]

In recent years, contamination of mineral oil hydrocarbons (MOH) in milk powder, especially infant formula, has become a public concern, and related international regulation has gradually escalated. However, there is no standard method for the determination of MOH in milk powder. In this paper, the sample pretreatment method based on the EU limits and analytical requirements were improved and optimized, and the saponification method, hexane extraction, silica gel clean-up, epoxidation reaction method in order were used, and a highly sensitive method for the determination of mineral oils of saturated hydrocarbons (MOSH) and mineral oils of aromatic hydrocarbons (MOAH) in milk powder by on-line high performance liquid chromatography-gas chromatography (HPLC-GC) were established. Results showed that, the method achieved a limit of quantification (LOQ) of 0.5 mg/kg and recoveries of 81.1%~112.0% (RSD=0.3%~3.8%), meeting the method requirements of the European Joint Research Center (JRC). The method was applied to analyze the international proficiency testing samples, and the results showed the detection results of MOSH and MOAH from C16 to C25 and C25 to C35 were close to the true values, and the absolute values of their z'-scores were less than 2. This indicated that the method passed the validation, and the method could be referred to as the standard for the determination of MOSH and MOAH in milk powder.

Mineral oil hydrocarbons (MOH) contain a wide structural diversity of molecules, for which the reference method of analysis is the online coupled liquid chromatography-gas chromatography with flame ionization detection (LC-GC-FID). These compounds are very heterogeneous from a toxicological viewpoint, and an accurate risk assessment when dealing with a MOH contamination can only be performed if sufficient information is available on the types of structures present (i.e., number of carbons, degree of alkylation, number of aromatic rings). Unfortunately, the separation performances of the current LC-GC-FID method are insufficient for such characterization, not even mentioning the possible coelution of interfering compounds which additionally hinder MOH determination. Comprehensive two-dimensional gas chromatography (GC × GC), while mostly used for confirmation purposes in the past, starts to prove its relevance for overcoming the weaknesses of the LC-GC method and reaching even better the analytical requirements defined in the latest EFSA opinion. The present paper therefore aims at highlighting how GC × GC has contributed to the understanding of the MOH topic, how it has developed to meet the requirements of MOH determination, and how it could play a role in the field for overcoming many of the current analytical and toxicological challenges related to the topic. [ABSTRACT FROM AUTHOR]

The goal of this work was to investigate the impact of refining on coconut oil particularly on the most toxicologically relevant fraction of the mineral oil aromatic hydrocarbon (MOAH) contamination, namely the fraction composed by the three to seven aromatic rings. A fully integrated platform consisting of a liquid chromatography (LC), a comprehensive multidimensional gas chromatography (GC) (LC-GC × GC) and flame ionization detector (FID) was used to obtained a more detailed characterization of the MOAH sub-classes distribution. The revised EN pr 16995:2017-08 official method was used for preparing the samples, both with and without the auxiliary epoxidation step. Crude coconut oil was spiked with different MOAH standards, namely naphthalenes, alkylated naphthalenes, benzo(a)pyrene, and its alkylated homologues. Refining was modelled by deodorization at 230 °C, stripping with 10 kg/h of steam under 1 mbar vacuum for 3 h. Complete removal of the naphthalenes and reduction of more than 98.8% of the benzo(a)pyrenes was observed. Epoxidation had a significant impact on the MOAH fraction with more than three rings, but with a high dependency on the sample matrix, being significantly less evident in the refined samples than in the crude ones. [ABSTRACT FROM AUTHOR]

ABSTRACT: The established analysis of mineral oil aromatic hydrocarbons (MOAH) provides results on the sum of all hydrocarbons with an aromatic moiety present in mineral oil contaminations. As MOAH substances are not believed to have equal toxicity, the European Food Safety Authority (EFSA) stated a need for a quantitative method for the determination of MOAH grouped according to the number of aromatic rings. The separation power of comprehensive two-dimensional gas chromatography (GC×GC) and the chromatographic grouping according to aromatic moieties renders quantification by means of flame ionization detection (FID) possible. A data processing method was established, which allows the subtraction of single peaks originating from the food and not considered to be MOAH. The quantification method was validated by spiking experiments and first results on 10 rice and 34 infant formula samples are given. The content of ≥3 ring MOAH in rice were in the range of 0.09–1.3 mg/kg, the contents for infant formula were below LOQ (between

A previous work dealt with surrogates and food simulants to evaluate mineral oil hydrocarbons (MOH) migration processes from paper‐based food packaging. In this article, we compare this study with migration studies of real papers, contaminated with MOH. The focus was the applicability of food simulants in contact with MOH and the verification of surrogates. Tenax and Sorb‐Star were chosen as food simulants, which were brought into contact with recycling paperboards. Kinetic studies were performed at 20°C, 40°C, and 60°C for up to 12 days. There were significantly lower migration rates for the more polar MOAH than for MOSH. There is nearly no migration of mineral oil aromatic hydrocarbons (MOAH) above C25. In general, Tenax in 'touching contact' showed the highest values, while Tenax tested with conditions that induce gas phase transport and Sorb‐Star resulted in lower but similar migration rates. Sorb‐Star in touching contact to the paperboard showed higher migration rates for non‐volatile compounds compared to Tenax in gas phase transfer, depending on the test temperature used. Nevertheless, under comparable conditions, MOH migrate to a similar percentual extent for each type of paperboard used. It was shown that the migration behaviour of MOH can be depicted by the use of respective surrogates, which will help to ease the analytical tasks. Migration tests with these surrogates using Tenax and Sorb‐Star as food simulants at 20°C and 40°C can cover a wide range of real‐life migration processes from paper‐based food packaging into foods, provided that appropriate conditions are chosen. [ABSTRACT FROM AUTHOR]

To determine the occurrence of mineral oil hydrocarbons (MOH) in food contact papers in China, and to investigate the potential sources of MOH contamination, a total of 159 food contact papers and raw materials were analysed by off-line solid-phase extraction-gas chromatography flame ionisation detection (SPE-GC-FID) and a GC-MS method. The migration of MOH from food contact papers into Tenax, olive oil or 50% ethanol under the worst foreseeable conditions of use was determined. The results indicated that the occurrence of MOH in China is of a potential health risk concerning the migration of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) which were detected in 82.6% and 50.4% of samples, respectively. Migration of MOSH from 47.9% of samples was higher than 2 mg/kg and migration of MOAH from 32.2% samples exceeded 0.5 mg/kg in case of the worst foreseeable condition of use. The highest mean migration of MOSH and MOAH were found in packaging papers for long-term storage (more than 6 months), with mean migration of 91.2 mg/kg and 1.4 mg/kg, respectively. Migration of MOH from printed paper was considerably higher than that of unprinted paper, validating previous findings that the printing ink is the predominant source of MOH contamination in food contact papers. Migration of MOH from paper bowls used for packing instant noodles was relatively low, suggesting the internal hollow layer may be acting as a functional barrier that could block the transfer of MOH (up to C28) through the gas phrase, even though the outer layer was made from recycled paper. High concentrations of MOSH and MOAH were also detected in de-foamers, adhesives and rosin sizing agents, indicating that the MOH contamination caused by the use of raw materials and additives should also be taken into consideration. [ABSTRACT FROM AUTHOR]

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Mineral oil hydrocarbons (MOH) are known to be mixtures of non-identified substances, which can migrate from, inter alia, recycled food packaging into food products. Such substances may have carcinogenic potential, which leads to a need to avoid their migration into food. In this article, we investigate the possible use of food simulants and model substances to simplify migration approaches. Tenax and Sorb-Star were chosen as simulant media. To stage the action of known components as a replacement for the migration of MOH, 16 single substances, including n-alkanes and aromatic compounds, were used. Kinetic studies were carried out at a maximum of 60°C with contact times of up to 14 days in touching contact with a medium or in gas-phase transfer to it. The results demonstrated that migration was predominantly a function of temperature, time and contact type, but it was also dependant on the molecular weight and polarity of the substances. Due to their low polarity, alkanes showed higher migration to the lipophilic food simulants than did pure aromatics without alkylation. Additionally, alkylated aromatics represent mineral oil aromatic hydrocarbons (MOAH) more realistically. In contrast to Tenax in the gas-phase transition, Tenax in touching contact may lead to overestimated values at higher temperatures. Migration values for Sorb-Star are in similar regions for both contact types. However, the values of the touching contact experiments were slightly higher than those of the gas-phase transfer. The results for Sorb-Star and Tenax with transport solely over the gas phase are also in good agreement. Sorb-Star generally represents an optimal simulant for chunky foods, whereas Tenax seems a good simulant for food types with a high contact surface. Temperatures up to 40°C are appropriate for most types of migration experiments, whereas 60°C should only be used as an option for experiments with Sorb-Star. [ABSTRACT FROM AUTHOR]

• Subfractionation of (mineral oil) aromatic hydrocarbons (MOAH) by number of aromatic rings (< 3 / ≥ 3 rings). • On-line implementation of a donor-acceptor complex chromatography (DACC) column into a common HPLC-GC-FID MOSH/MOAH setup. • Introduction of new internal standards for method verification and quantification of aromatic hydrocarbons. • Validation and comparison of fractionation results with comprehensive two-dimensional gas-chromatography (GCxGC). • Application of DACC-HPLC-GC-FID approach to mineral oil products and food samples (e.g., rice, infant formula). An automated implementation for a subfractionation of mineral oil aromatic hydrocarbons (MOAH) into a mono-/di-aromatic fraction (MDAF) and a tri-/poly-aromatic fraction (TPAF) is presented, which is highly demanded by the European Food Safety Authority (EFSA) respecting the genotoxic and carcinogenic potential of MOAH. For this, donor-acceptor-complex chromatography (DACC) was used as a selective stationary phase to extend the conventional instrumental setup for the analysis of mineral oil hydrocarbons via on-line coupled liquid chromatography-gas chromatography-flame ionization detection (LC-GC-FID). A set of six new internal standards was introduced for the verification of the MOAH fractionation and a quantification of MDAF and TPAF, respectively. The automated DACC approach was applied to representative petrochemical references as well as to food samples, such as rice and infant formula, generally showing well conformity with results obtained by state-of-the-art analysis using two-dimensional GC (GCxGC). Relative deviations of DACC/LC-GC-FID compared to GCxGC-FID methods regarding the ≥ 3 ring MOAH content ranged between -50 and +6 % (median: -2 %, all samples, only values above limit of quantification). However, crucial deviations mainly result from "border-crossing" substances, e.g., dibenzothiophenes or partially hydrogenated MOAH. These substances can cause overestimations of ≥ 3 ring MOAH fraction during GCxGC analysis due to co-elution, which is mostly avoided using the DACC approach. Furthermore, the DACC approach can help to minimize underestimations of toxicologically relevant ≥ 3 ring MOAH caused by an unavoidable loss of MOAH during epoxidation, since natural olefins, such as terpenes, predominantly elute in MDAF, which was exemplarily shown for an olive oil and a terpene reference. The presented approach can be implemented easily in existing LC-GC-FID setup for an automated and advanced screening of MOAH to lower the need for elaborate GCxGC analysis also in routine environments. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A quantitative 1H NMR method for analyzing mineral oil hydrocarbons was developed. • Paraffin samples were analyzed using the ratio of aromatic to aliphatic protons. • Characteristics of purification, refinement, and aromatic traces were evaluated. Abstract • Mineral oil hydrocarbons incorporated in pharmaceutical preparations are frequently administered to the skin as creams and/or ointments. However, the oral route is also of interest when the substances are used in form of medicated lip sticks or for the polishing of coated tablets. In Europe, the substances are monographed by the European Pharmacopoeia as Liquid Paraffin, Light Liquid Paraffin, White Soft Paraffin, Yellow Soft Paraffin, and Hard Paraffin. The consistency differs from liquid and semi-solid to solid and influences the functional characteristics. Because these excipients are produced from petroleum, they contain residual traces of aromatic compounds. Therefore, the European Pharmacopoeia tests the substances on residual impurities of condensed poly aromatic hydrocarbons. Recently, the question arose whether these tests are fully sufficient, since toxic condensed polyaromatic hydrocarbons are only one type of aromatic compounds found in mineral oil hydrocarbons. Especially aliphatic hydrocarbons containing isolated spots of aromatic cores are not in the focus of compendial tests. Therefore, combined chromatographic methods were developed and should resolve this problem by a separation of the different aromatic impurities. Because these chromatographic techniques involve several steps and the interpretation of the result is difficult, we established a quantitative 1H NMR spectroscopic method for the determination of aromatic traces in mineral oil hydrocarbons. The technique is a holistic approach for all traces of aromatic hydrocarbons. The technique was tested with several samples collected from different stages of the refinement process and in addition with different excipient samples from the market. Moreover, a few samples of synthetic paraffin made by the Fischer-Tropsch process were analyzed. The results reveal the purification characteristics of the refinement and the differences in the aromatic impurities. [ABSTRACT FROM AUTHOR]

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography-gas chromatography-flame ionisation detection (online HPLC-GC-FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7-45% in dry foodstuffs and 4-48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (˂C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (˂C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a 'crispy' product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C20-C35. [ABSTRACT FROM AUTHOR]

Work on mineral oil hydrocarbons (MOH) contaminating food is reviewed up to about 2010, when the subject received broad publicity. It covers the period of the main discoveries and elimination or reduction of the dominant sources: release agents used in industrial bakeries, spraying of rice, additions to animal feed, contamination of edible oils from various sources and migration from paperboard packaging. In most cases, highly refined (‘white’) oils were involved, but also technical oils, e.g. from the environment, and more or less crude oil fractions from jute and sisal bags. There were numerous unexpected sources, and there might still be more of those. The exposure of the consumers to MOH must have been markedly reduced in the meantime. Environmental influx may have become dominant, particularly when taking into account that these MOH go through several degradation processes which might enrich the species resisting metabolic elimination. Major gaps are in the systematic investigation of sources and the largely unavoidable levels from environmental contamination, but also in the toxicological evaluation of the various types of hydrocarbons. A regulation is overdue that avoids the present discrepancy between the low tolerance to MOH perceived as contaminants and the very high legal limits for some applications - the MOH are largely the same. [ABSTRACT FROM AUTHOR]

On-line coupled high performance liquid chromatography-gas chromatography-flame ionization detection (HPLC-GC-FID) is the most widely used method for the analysis of mineral oil hydrocarbons in food, food contact materials, tissues and cosmetics. With comprehensive two-dimensional gas chromatography (GCxGC), a tool became available for better establishing the elution sequence of the various types of hydrocarbons from the HPLC column used for isolating the mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The performance of a heavily used HPLC column with reduced retention for MOAH was investigated to improve the robustness of the method. Updates are recommended that render the MOSH/MOAH separation less dependent of the state of the HPLC column and more correct in cases of highly refined mineral oil products of high molecular mass. Cyclohexyl cyclohexane (Cycy), used as internal standard, turned out to be eluted slightly after cholestane (Cho); apparently the size exclusion effect predominates the extra retention by ring number on the 60 Å pore size silica gel. Hence, Cycy can be used to determine the end of the MOSH fraction. Long chain alkyl benzenes were eluted earlier than tri-tert. butyl benzene (Tbb). It is proposed to start the MOAH transfer immediately after the MOSH fraction and use a gradient causing breakthrough of dichloromethane (visible in the UV chromatogram) at a time suitable to elute perylene (Per) at the end of the fraction. In this way, a decrease in retention power of the HPLC column can be tolerated without adjustment of the MOAH fraction until some MOAH start being eluted into the MOSH fraction. This critical point can be checked either with di(2-ethylhexyl) benzene (DEHB) as a marker or the HPLC-UV chromatogram. Finally, based on new findings in rats and human tissues, it is recommended to integrate the MOSH and MOAH up to the retention time of the n -alkane C40. [ABSTRACT FROM AUTHOR]

A high throughput, high-sensitivity procedure, involving simultaneous microwave-assisted extraction (MAS) and unsaponifiable extraction, followed by on-line liquid chromatography (LC)–gas chromatography (GC), has been optimised for rapid and efficient extraction and analytical determination of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in cereal-based products of different composition. MAS has the advantage of eliminating fat before LC–GC analysis, allowing an increase in the amount of sample extract injected, and hence in sensitivity. The proposed method gave practically quantitative recoveries and good repeatability. Among the different cereal-based products analysed (dry semolina and egg pasta, bread, biscuits, and cakes), egg pasta packed in direct contact with recycled paperboard had on average the highest total MOSH level (15.9 mg kg −1 ), followed by cakes (10.4 mg kg −1 ) and bread (7.5 mg kg −1 ). About 50% of the pasta and bread samples and 20% of the biscuits and cake samples had detectable MOAH amounts. The highest concentrations were found in an egg pasta in direct contact with recycled paperboard (3.6 mg kg −1 ) and in a milk bread (3.6 mg kg −1 ). [ABSTRACT FROM AUTHOR]

Many foods are contaminated by hydrocarbons of mineral oil or synthetic origin. High performance liquid chromatography on-line coupled with gas chromatography and flame ionization detection (HPLC–GC-FID) is a powerful tool for the quantitative determination, but it would often be desirable to obtain more information about the type of hydrocarbons in order to identify the source of the contamination and specify pertinent legislation. Comprehensive two-dimensional gas chromatography (GC × GC) is shown to produce plots distinguishing mineral oil saturated hydrocarbons (MOSH) from polymer oligomeric saturated hydrocarbons (POSH) and characterizing the degree of raffination of a mineral oil. The first dimension separation occurred on a phenyl methyl polysiloxane, the second on a dimethyl polysiloxane. Mass spectrometry (MS) was used for identification, FID for quantitative determination. This shows the substantial advances in chromatography to characterize complex hydrocarbon mixtures even as contaminants in food. [ABSTRACT FROM AUTHOR]

Mineral oil is an ubiquitous food contaminant potentially toxic. It is generally divided into aromatic hydrocarbons (MOAH) and saturated hydrocarbons (MOSH). These compounds are currently under investigation by the European Union to determine their occurrence and their toxicity before legislating on the matter. Although the discussion mainly focuses on food, animal feed can indirectly contribute to human exposure to such a contaminant. In this study, seven commercial feeds were analyzed. The analyses were carried out in two different Universities (Udine-IT and Liège-BE), performing the same sample preparation protocol: microwave-assisted saponification and extraction followed by epoxidation for the MOAH fraction. The final determination was performed by hyphenated liquid-gas chromatography (LC-GC) and LC coupled to comprehensive multidimensional gas chromatography (LC-GC × GC) with parallel detection, namely flame ionization detector (FID) and time-of-flight mass spectrometer (ToFMS). The results obtained by the two laboratories were generally in good agreement. The results obtained by LC-GC × GC-ToFMS/FID platform provided consistent results, with the advantages of more robust data interpretation that can compensate for problems occurring during purification. Moreover, the coupling of enhanced separation obtained by GC × GC and the MS information allowed for a more in-depth characterization of the contamination. [ABSTRACT FROM AUTHOR]

Highlights: [•] MOSH and MOAH determination in dry food using PLE followed by on-line LC–GC. [•] PLE for selective extraction of superficial contamination (mainly from packaging). [•] PLE method for determining total contamination. [•] Method performances and comparison with classical solvent extraction. [•] Applications to pasta and rice samples. [Copyright &y& Elsevier]

Abstract: Packaging can represent a primary source of food contamination with mineral oil saturated hydrocarbons (MOSH) and aromatic hydrocarbons (MOAH), especially when recycled cardboard or mineral oil based printing inks are used. A pressurized liquid extraction (PLE) method, followed by on-line LC–GC analysis, has been optimized for rapid mineral oil determination in cardboard and paper samples. The proposed method involves extraction with hexane (2 cycles) at 60°C for 5min, and allows for the processing of up to 6 samples in parallel with minimal sample manipulation and solvent consumption. It gave good repeatability (coefficient of variation lower than 5%) and practically quantitative extraction yield (less than 2% of the total contamination found in a third separate cycle). The method was applied to different cardboards and paper materials intended for food contact. Results obtained were similar to those obtained by applying classical solvent extraction with hexane/ethanol 1:1 (v/v) as described by Lorenzini et al. [20]. [Copyright &y& Elsevier]

Migration from recycled paperboard was monitored after 2, 4 and 9 months of storage for six test foods industrially packed in five configurations, four with internal plastic films. After 9 months, the migration of mineral oil saturated hydrocarbons into foods directly packed in the paperboard amounted to 30–52 mg/kg, which corresponded to 65%–80% of those of a volatility up to that of then-alkane C24in the paperboard. The concentration of the migrated aromatic hydrocarbons in the foods ranged from 5.5 to 9.4 mg/kg. More than half of this migration occurred in the first 2 months. Differences between the foods amounted to mostly less than a factor of 2 and seemed to be related to porosity or permeability more than fat content. Nine photoinitiators were detected in the paperboard, of which eight migrated into the packed food at up to 24%. Several plasticisers were present in the recycled paperboard, but only butyl phthalates showed significant migration. After 9 months, up to 40% of diisobutyl phthalate and 20% of dibutyl phthalate migrated into the food with direct contact. The internal polyethylene film hardly slowed migration, but the film and the tray absorbed approximately three times more mineral oil than the food, despite constituting merely 4% of the mass of the pack. Oriented polypropylene strongly slowed migration: The highest migration of saturated hydrocarbons measured after 9 months (2.3 mg/kg) corresponded to only 3% of the content in the paperboard and included migrated polyolefin oligomeric saturated hydrocarbons. Coating of polypropylene with an acrylate further slowed the migration, but the migration from the paperboard was still detectable in four of the six samples. Polyethylene terephthalate was a tight barrier. [ABSTRACT FROM AUTHOR]

Highlights: [•] Analysis of mineral oil (both MOSH and MOAH fractions) in food products. [•] Use of a comprehensive gas chromatographic system (GC×GC), with dual detection (FID and MS). [•] Silver nitrate silica gel solid-phase extraction (SPE) cartridge was exploited for sample preparation. [•] Comparison of quantitative results obtained via GC×GC, off-line GC-FID, and on-line liquid–gas chromatography (LC–GC). [ABSTRACT FROM AUTHOR]

Abstract: So far the majority of the measurements of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) were obtained from on-line high performance liquid chromatography–gas chromatography–flame ionization detection (on-line HPLC–GC–FID). Since this technique is not available in many laboratories, an alternative method with more easily available tools has been developed. Preseparation on a small conventional liquid chromatographic column was optimized to achieve robust separation between the MOSH and the MOAH, but also to keep out the wax esters from the MOAH fraction. This was achieved by mixing a small portion of silica gel with silver nitrate into highly activated silica gel and by adding toluene into the eluent for the MOAH. Toluene was also added to the MOSH fraction to facilitate reconcentration and to serve as a keeper preventing loss of volatiles during solvent evaporation. A 50μl volume was injected on-column into GC–FID to achieve a detection limit for MOSH and MOAH below 1mg/kg in most foods. [Copyright &y& Elsevier]

Abstract: Mineral oil hydrocarbons are complex as well as varying mixtures and produce correspondingly complex chromatograms (on-line HPLC–GC-FID as described in Part 1): mostly humps of unresolved components are obtained, sometimes with sharp peaks on top. Chromatograms may also contain peaks of hydrocarbons from other sources which need to be subtracted from the mineral oil components. The review focuses on the interpretation and integration of chromatograms related to food contamination by mineral oil from paperboard boxes (off-set printing inks and recycled fibers), if possible distinguishing between various sources of mineral oil. Typical chromatograms are shown for relevant components and interferences as well as food samples encountered on the market. Details are pointed out which may provide relevant information. Integration is shown for examples of paperboard packaging materials as well as various foods. Finally the uncertainty of the analysis and limit of quantitation are discussed for specific examples. They primarily result from the interpretation of the chromatogram, manually placing the baseline and cuts for taking off extraneous components. Without previous enrichment, the limit of quantitation is between around 0.1mg/kg for foods with a low fat content and 2.5mg/kg for fats and oils. The measurement uncertainty can be kept clearly below 20% for most samples. [Copyright &y& Elsevier]

Abstract: For the analysis of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH), on-line coupled high performance liquid chromatography–gas chromatography–flame ionization detection (HPLC–GC–FID) offers important advantages: it separates MOSH and MOAH in robust manner, enables direct injection of large aliquots of raw extracts (resulting in a low detection limit), avoids contamination of the sample during preparation and is fully automated. This review starts with an overview of the technology, particularly the fundamentals of introducing large volumes of solvent into GC, and their implementation into various transfer techniques. The main part deals with the concepts of MOSH and MOAH analysis, with a thorough discussion of the choices made. It is followed by a description of the method. Finally auxiliary tools are summarized to remove interfering components, enrich the sample in case of a high fat content and obtain additional information about the MOSH and MOAH composition. [Copyright &y& Elsevier]

Abstract: A rapid off-line solid phase extraction-large volume injection-gas chromatography-flame ionisation detection (SPE-LVI-GC-FID) method, based on the use of silver silica gel and low solvent consumption, was developed for mineral oil saturated hydrocarbon (MOSH) and mineral oil aromatic hydrocarbon (MOAH) determination in cardboard and dried foods packaged in cardboard. The SPE method was validated using LVI with a conventional on-column injector and the retention gap technique (which allowed to inject up to 50μL of the sample). Detector response was linear over all the concentration range tested (0.5–250μg/mL), recoveries were practically quantitative, repeatability was good (coefficients of variation lower than 7%) and limit of quantification adequate to quantify the envisioned limit of 0.15mg/kg proposed in Germany for MOAH analysis in food samples packaged in recycled cardboard. Rapid heating of the GC oven allowed to increase sample throughput (3–4 samples per hour) and to enhance sensitivity. The proposed method was used for MOSH and MOAH determination in selected food samples usually commercialised in cardboard packaging. The most contaminated was a tea sample (102.2 and 7.9mg/kg of MOSH and MOAH below n-C25, respectively), followed by a rice and a sugar powder sample, all packaged in recycled cardboard. [Copyright &y& Elsevier]

Party plates made of recycled paperboard with a polyolefin film on the food contact surface (more often polypropylene than polyethylene) were tested for migration of mineral oil into various foods applying reasonable worst case conditions. The worst case was identified as a slice of fried meat placed onto the plate while hot and allowed to cool for 1 h. As it caused the acceptable daily intake (ADI) specified by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) to be exceeded, it is concluded that recycled paperboard is generally acceptable for party plates only when separated from the food by a functional barrier. Migration data obtained with oil as simulant at 70°C was compared to the migration into foods. A contact time of 30 min was found to reasonably cover the worst case determined in food. [ABSTRACT FROM AUTHOR]

Recycled paper and board used in food packaging materials (boxes, paper bags) often cause migration of mineral oil into food at levels which are unacceptable according to present toxicological assessments. When foods in recycled board are densely packed into larger boxes or onto pallets, most of the hydrocarbons up to n-C20 may migrate into the packed food within a few weeks, those up to n-C28 at a decreasing rate. Unprinted recycled board contained 300–1,000 mg/kg mineral oil < n-C28. The main sources are the inks used for printing newspapers: newspapers contained roughly 3,000 mg/kg mineral oil < n-C28. These mineral oils fall into classes for which JECFA established a tolerable daily intake of 0.01 mg/kg body weight. Using standard assumptions for calculating specific migration limits, a maximum tolerable concentration in food of 0.6 mg/kg is derived. This evaluation assumes highly refined white oils, whereas the oils found in recycled board are of technical quality and contain 15–25% aromatic compounds, predominantly with 1–3 aromatic rings, as shown by comprehensive GC × GC. This finding precipitates authorities into a dilemma: recycling is supported for the sustainable use of materials, but on the basis of present toxicological assessments the migration is often far beyond acceptable. [ABSTRACT FROM AUTHOR]

Key issues around the evaluation of risks to humans from mineral oils in food and feedstuffs are discussed. MOHs (MOAH and MOSH) occur in food due to intentional use, contamination from environmental sources and during transport/processing, or through migration from food contact materials. Problems in setting and enforcing human health guidelines for MOH include uncertainty around MOH toxicity and the specialist expertise needed for analysis of complex food matrices. Currently, the method of choice for measuring mineral oils is LC-GC-FID, however some complex food matrices also require additional analytical techniques to differentiate between some naturally occurring hydrocarbons and those from other sources, including of petrogenic origin. This requires the skills of an experienced analyst. Significant toxicological gaps for MOHs prevent robust human health risk assessment and the derivation of guidance values. As food-grade mineral oils are virtually MOAH-free, the key issue explored here is the relevance to humans of liver (micro)granulomas observed in F344 rats following oral intake. Available data suggest that despite the ubiquitous nature of MOH in the human diet, the prevalence of liver lipogranulomas in the population is low. These are not associated with inflammation and based on current evidence are not considered of human health significance. • MOHs are complex mixtures, historically characterised on physical properties, not chemical structures/molecular weight. • The method of choice for the routine quantification of mineral oils, LC-GC-FID, is sometimes not sufficient for the characterisation of complex food matrices. • Toxicological studies in F-344 and Sprague-Dawley rats show very different sensitivities to the adverse effects of MOSH. • Differences in sensitivities between rat strains are likely due to variation in absorption and accumulation of MOSH. • Characterisation of MOH used in early toxicity studies is often poor, impacting on their use for evaluating food safety. [ABSTRACT FROM AUTHOR]

The evaluation of mineral oils by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) provided high acceptable daily intakes for classes largely falling into the mass range strongly accumulated by humans. Because they are roughly 2 orders of magnitude above the present exposure, they authorize strongly increased exposure. An approach based on accumulation seems more adequate. Increased organ weights might be more critical than granulomas. Aromatic hydrocarbons with 1-2 aromatic rings should be distinguished from those with at least 3 aromatic rings. If mineral oil saturated hydrocarbon limits were low, no limit might be needed for the 1-2 ring aromatics. It should be considered to phase out substantial use of mineral oils in food application.