WPD Scientific News Service Modern NUTRITION TODAY PUBLISHER: No. 4 /July 2016 Publisher: Prof. Dr. Reinhard Matissek – Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI), Cologne Minimisation of Mineral Oil Components in Foods Research project to identify sources of migration and minimisation measures Prof. Dr. Reinhard Matissek, Anna Dingel, Julia Schnapka, Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI), Cologne www.lci-koeln.de 1www.bdsi.de /20 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY 4/2016 Minimisation of Mineral Oil Components in Foods Research project to identify sources of migration and minimisation measures Prof. Dr. Reinhard Matissek, Anna Dingel, Julia Schnapka, Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI), Cologne SUMMARY Mineral oil components occur in the environment all around us and can therefore migrate into foods in very different ways. These components primarily involve mineral oil saturated hydrocarbons (MOSH) and, to a lesser degree, mineral oil aromatic hydrocarbons (MOAH). MOSH are easily absorbed from foods and can accumulate in human fat tissues and various organs. The toxicological effects of MOSH and MOAH can only be derived from animal experiments because there are currently no studies on humans available. It is recommended to minimise the intake of MOSH and MOAH as much as possible. The main source of migration of mineral oil components into both raw materials and foods is not caused by the food industry itself but rather by recycled cardboard boxes, paper and corrugated cardboards as well as jute bags. Through targeted measures such as switching to fresh fibres, the use of mineral-oil-free printing inks, and/or the introduction of suitable barriers, manufacturers have already optimised many product packaging solutions and hence reduced the migration of mineral oil components. However, it would ultimately be more effective if newspaper publishers used mineral-oil-free printing inks in order to close off the migration of mineral oil components in the recycling loop. During the transport and storage of raw materials, it is also important that the material used (e. g., cardboard boxes, paper and jute bags) does not provide a source of migration for MOSH/MOAH. The participation of all stakeholders – from the farming sector to the raw materials trade, the transportation sector, the food industry, the packaging industry, food traders, and the printing ink industry, including newspaper publishers, – is required to minimise mineral oil components in foods. A current research project of the Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI) has significantly helped to gain more insights. The project culminated in a comprehensive catalogue of possible minimisation measures. www.lci-koeln.de www.bdsi.de 2/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY INTRODUCTION Over the last few years various foods have been found to contain traces of mineral oil components. These components are a complex mixture that primarily involve mineral oil saturated hydrocarbons (MOSH) and, to a lesser degree, mineral oil aromatic hydrocarbons (MOAH). Both MOSH and MOAH occur in the environment all around us. This is not surprising considering the amount of mineral oil that is being used. According to the International Energy Agency (IEA), approximately 15 billion litres of mineral oil were consumed daily in 2015, most of which was burned [1]. Correspondingly, there are multiple ways in which mineral oil components can migrate into foods. The fact that mineral oil components can migrate into foods was discovered by research done at the Zurich Canton Laboratory/Switzerland [2]. At that time the cause was identified as cardboard made from recycled newspapers which has now been determined as the main source. Recycled cardboard contains mineral oil based printing inks commonly used in newspaper printing. According to the German Federal Environment Agency (UBA) over 60,000 tonnes of mineral oil are transferred annually to the European recycling loop via this source alone [3]. MOSH/MOAH from recycled cardboards, paper and corrugated cardboards can migrate into foods by way of their vaporisation. The initial findings concerned dry foods with a large surface area (e. g., rice, oatmeal, flour, and pasta) that were packaged directly in paper or cardboard. Fatty foods (e. g., pizza) were later also found to be affected. Mineral oil components are even found in plantand animal-based foods that were not packaged in paper or cardboard. The efforts required to minimise MOSH/MOAH in foods are immense. This is because there are numerous possible sources of migration along the food processing chain – from harvest and transport to the processing and storage of raw materials and 4/2016 foods – and because many different stakeholders are involved in this chain worldwide. Moreover, the scientific analysis of MOSH and MOAH is extremely challenging. In order to identify and close off additional sources of migration and also to optimise their own internal analytics, the Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI) began a three-year scientific research project into the “Minimisation of MOSH/ MOAH in foods” in 2013. This has led to good results and practical outcomes. What are MOSH and MOAH? Mineral oil primarily consists of hydrocarbons which can be divided into two chemically and structurally different fractions: MOSH and MOAH. Both fractions include a wide variety of compounds with carbon chains ranging from 10 to 50 atoms long. MOSH are saturated paraffinic, i.e. open-chain, often branched and naphthene (cyclic) hydrocarbons with low to medium viscosity. MOAH include various aromatic hydrocarbons, which mainly consist of one to four ring systems and are up to 97% alkylated. How do mineral oil components MIGRATE inTO food? Mineral oil components are ubiquitous, i. e. they occur in the environment all around us. Therefore an environment-related “background level contamination” of food raw materials with mineral oil hydrocarbons is given, e. g. caused by combustion processes (including engine emissions, emissions from energy supply and industrial plants, etc.) as well as particulate matter from paved roads. During harvest, mineral oil components can migrate into foods via pesticides or lubricating/hydraulic oils from harvesting machinery. The treatment of crops with mineral-oil-based substances, e. g. anti-foam/ release agents, or – as in the case of soybeans – www.lci-koeln.de www.bdsi.de 3/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY dust-binding agents (antidusting), or special spray for gloss, is another possible source. Furthermore, MOSH/MOAH can also migrate into foods during the processing of raw materials, e. g. through oiling machine parts or grease used in maintenance and repair work [4, 5]. Other sources of migration are certain registered food additives and processing aids used in all areas of food processing. In these cases, migration is often limited to the MOSH fraction because purified products (e. g. wax) originating from mineral oils are involved. Figure 1 displays the various potential sources of migration discovered by the research project of the BDSI/LCI – a milestone in its field. Additives Processing Aids Migration Primary Products Cultivation/ Harvest Commodity Trading End Products Production Food Trade Contamination Figure 1: Research milestone – discovery of the various potential sources of migration for mineral oil hydrocarbons into raw materials and foods. The research project also confirmed that jute and sisal bags used for transporting and storing both raw materials and foods presented another source of migration (see also text in box as well as Figure 2). 3 However, the main sources of migration are cardboard boxes, cardboards and corrugated cardboard made from recycled fibres. The latter are used as socalled dressings (e. g. for lining ship containers) to control humidity (Figure 3). Recycled cardboard can 4/2016 Jute and sisal bags are often used to transport food raw materials. The fibres are treated with batching oils to facilitate the production of bags. In 1998 already, the International Jute Organization (IJO) issued a recommendation for the purity requirements of batching oils [6]. According to this, jute bags coming into contact with specific foods may only be manufactured using suitable vegetable oils and may not contain toxic components. Furthermore, they may not transfer off-flavours or off-tastes to foods. In addition to the general requirements, for jute bags intended to transport and store cacao beans, coffee beans, and nuts, the IJO specified a maximum value of unsaponifiable components of < 1.250 mg/kg of jute fibres. The measurement of the unspecific sum parameter ‘unsaponifiables’ was selected back then so that in countries producing jute bags, the IJO recommendation could be easily tested by using simple laboratory equipment, instead of the otherwise costly mineral oil hydrocarbon analysis requiring complex devices. In 2004, in its statement on the use of batching oils in jute and sisal bags, the European Food Safety Authority (EFSA) confirmed the aforementioned recommendation of the IJO from a toxicological perspective [7]. However, in light of the persisting MOSH/MOAH contents (Figure 2), those responsible should ensure that the guidelines are applied and implemented, i. e. that bags produced for the food industry should not contain any mineral oil components. also contain mineral oil components from the printing inks used in newspaper printing. These components by way of their vaporization are transferred from the cardboard packaging to raw materials and foods. In addition to recycled cardboard, the adhesives/ hotmelts used to produce packaging and the printing inks used to print packaging, both of which www.lci-koeln.de www.bdsi.de 4/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY MOSH (blue), MOAH (red) Figure 2: The box-plot representation of the MOSH/MOAH contents in jute and sisal bags shows the interquartile range defined by the 25th and 75th percentiles (box) as well as the maximum and minimum of the data set. 4/2016 In the case of dry food stored at room temperature, mineral oil hydrocarbons migrate into foods via vaporisation, transport in the gas phase, and recondensation. This is limited to compounds with a certain vapor pressure (e. g. hydrocarbons < C24). Inner packaging made of paper, polyethylene (PE), or polypropylene (PP) can delay the migration but not completely prevent it. Only packaging that contains aluminium and polyethylene terephthalate (PET) as well as special films are considered to be migration-proof functional barriers [9, 10]. However, these also have disadvantages. Not only is the production of aluminium foil for inner bags or the coating of cardboard energy-intensive but also detrimental to the recycling process and therefore a strain on the environment. Moreover, the use of contain mineral oils, were identified as sources of migration for mineral oil components. Packaging manufacturers now switch to cardboard made from fresh fibres, print with mineral-oil-free printing inks, and introduce suitable protective barriers, such as films. However, this only partially solves the problem as mineral oil components from additional transport cardboard packaging, from dressings, or from adjacent packages in warehouses or households can still migrate into foods. As part of the research project of the BDSI/LCI, many raw materials were analysed with respect to their MOSH/MOAH content. It was shown, for example, that cocoa beans do not naturally contain MOSH/MOAH [8], which means that these substances can only migrate into the raw materials/ foods during transport and storage along the food processing chain. The same applies to nearly all raw materials, especially those that are transported and stored in a similar manner. Figure 4 shows the results of a few analysed raw materials. While MOSH/POSH contents were measured in many raw materials (for POSH, see the section “Analysis” on page 7, it was only possible to quantify MOAH in certain groups of raw materials (e.g., coffee beans, cacao masses, vegetable fats, and spices). MOSH (blue), MOAH (red) Figure 3: The box-plot representation of the MOSH/MOAH contents in recycled cardboard and dressings (corrugated cardboard for lining transport containers) shows the interquartile range defined by the 25th and 75th percentiles (box) as well as the maximum and minimum of the data set. films impermeable to water vapor can also lead to increased bacterial growth in food as well as the loss of crispiness in baked goods [9]. The development of MOSH/MOAH-proof films or coatings is currently the subject of intensive research in the packaging industry. They are necessary since product-specific quality requirements must be considered. www.lci-koeln.de www.bdsi.de 5/ 11 WPD Scientific newS Service MoDern nUtrition toDAY 4/2016 Figure 4: The box-plot representation of the MOSH/POSH and MOAH contents in various raw materials shows the interquartile range defined by the 25th and 75th percentiles (box) as well as the maximum and minimum of the data set (sorted according to ascending MOSH/POSH medians; POSH = polyolefin oligomeric saturated hydrocarbons, which cannot be analytically distinguished from MOSH) . HEALTH RISk ASSESSMENT, UPTAkE, AND RECOMMENDATIONS Mineral oil hydrocarbons such as MOSH and MOAH are easily absorbed by the human body (up to 90%). It has been proven that MOSH with a chain length ranging from 16 carbon atoms (C16) up to C35 or higher accumulate in human fat tissues and various organs [2, 4, 11]. In contrast, MOSH with a hydrocarbon chain length of less than C16 do not accumulate in the human body [4, 12]. The Federal Institute for Risk Assessment (BfR) therefore derived a guideline value of 12 mg/kg food for the tolerable migration of MOSH with a hydrocarbon chain length from C10 to C16 to foods. For a chain length from C16 to C20, this value equals to 4 mg/kg [13, 14]. According to the BfR, the migration of MOSH should be minimised as much as technically possible. Since MOAH predominantly consist of alkylated aromatic hydrocarbons, the BfR believes that it cannot be dismissed that those fractions also can contain carcinogenic substances. Thus, a detectable migration of MOAH in foods should not take place [14]. The estrogenic effects of MOAH were demonstrated in animal studies [15]. Up to now, no toxicological studies on the effects of absorbed mineral oil components on humans are available [14]. www.lci-koeln.de www.bdsi.de 6/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY With respect to the uptake of mineral oil components, in a recent estimate from May 2012, the EFSA assumes a daily MOSH absorption of 0.03–0.3 mg/kg body weight in adults. The rate of uptake can be even higher in children [4]. According to the estimates of the EFSA, the resorption of aromatic hydrocarbons (MOAH) is approximately 20% of that for MOSH (i.e. 0.006–0.06 mg/kg body weight per day). There are currently no legal guidelines that regulate the content of mineral oil components in foods. Due to insufficient data, the Joint FAO/WHO Expert Committee on Food Additives (JECFA) withdrew the temporary ADI (acceptable daily intake) in 2012. The analysis of MOSH and MOAH is a difficult task Determining the content of mineral oil components in foods can be challenging, especially since it is a complex mixture that must be quantified as the sum of all its components. Because of the huge number of compounds, the analysis of individual components is not possible. That is why the gasphase chromatographic analysis of complex mineral oil mixtures results in very broad signals instead of sharp peaks. In such cases, analytic chemists speak of chromatographic humps (or unresolved complex mixtures – UCM; see Figure 5). 4/2016 Based on the current technology, MOSH and MOAH can be most reliably analysed using an on-line coupled liquid chromatography-gas chromatography flame ionisation detector (LC-GC-FID). At the international level, researchers are currently developing a standardised reference analysis method, which is verified in inter-laboratory tests. A standard entitled “Foodstuffs – vegetable oils and foods based on vegetable oil – determination of mineral oils from saturated hydrocarbons (MOSH) and aromatic hydrocarbons (MOAH) with on-line HPLC-GC-FID (DIN EN 16995)” has been drafted. The standard is important for reliably comparing values measured in different laboratories. The analysis is further complicated by polyolefin oligomeric saturated hydrocarbons (POSH), which are MOSH-like structures that can migrate from polyethylene (PE) or polypropylene (PP) films into foods. These cannot be readily distinguished from MOSH. A comprehensive gas chromatography coupled with time-of-flight mass spectroscopy (GC x GC ToF-MS) can be helpful in this respect. This particularly complex high-tech measurement method is commonly used in the Food Chemistry Institute (LCI). Voltage „Hump“ Figure 5: Representation of a chromatographic hump. Here: MOSH chromatogram of a sample from recycled cardboard. www.lci-koeln.de www.bdsi.de 7/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY Possibilities for minimising MOSH and MOAH in foods From the perspective of the BfR, the Federal Ministry of Food and Agriculture (BMEL), the UBA, and the food industry, one of the main sources of migration of mineral oil components into foods could be closed off by using mineral-oil-free printing inks based on vegetable oils in newspaper printing. According to the UBA, in the EU alone the annual transfer of more than 60,000 tonnes of mineral oil to the recycling loop could be effectively prevented at a comparatively low total cost [16]. Although tackling the problem at its source would be the most effective, and even though printing inks based on vegetable oil are already available, the newspaper industry has not yet made any changes. The food industry has been working for years to minimise the migration of MOSH/MOAH in those areas in which they can exert a direct influence. Also the paper industry has been addressing the problem for quite some time. Seeing as much has been undertaken in the past and still a lot is currently being done on a national level, German products perform relatively well in international comparisons. The following approaches for reducing mineral oil components in foods have already been implemented, tested, or are possible: •Many food producers have started using fresh fibre cardboard instead of recycled cardboard for packaging. However, this is only a partial solution: mineral oil components can also migrate to raw materials and foods from jute and sisal bags, transport packaging, corrugated cardboard used to line transport containers or from adjacent cardboard packaging. Moreover, the UBA does not prefer this solution as the use of recycled paper is more environmentally friendly and sustainable. •The food industry has also switched to mineral-oil-free printing inks for printing packaging. 4/2016 •The introduction of suitable barriers between foods and packaging cardboard (e. g. coating of the inside of the carton with composite film or the use of inner bags). Since product-specific quality requirements must be considered, the development of MOSH/MOAH-proof films or coatings is currently the subject of intensive research in the packaging industry. There are, however, some disadvantages, including a greater strain on the environment since composite packaging is not readily recycled and because aluminium production is energy-intensive. Films impermeable to water vapour can also lead to increased bacterial growth in food as well as the loss of crispiness in baked goods. Like special films, they are not appropriate for all foods. •The paper industry has already reduced the use of recycled paper containing high levels of mineral oil in the production of cardboard boxes. •The food industry and the suppliers of raw materials demand the consistent implementation of the IJO recommendations on the treatment of jute and sisal bags, i. e. exclusive treatment with mineral-oil-free batching oils based on vegetable oils as well as the use of mineral-oil-free printing inks for labelling bags. The German Confectionery Industry has intensified its research The migration of mineral oil components affects nearly all foods – including those in the confectionery industry. The BDSI has therefore intensified its activities for consumer health protection. As described above, in its three-year research project, the BDSI-owned, internationally recognised Food Chemistry Institute (LCI) has focused on the analysis of MOSH/MOAH, its migration sources, and prevention strategies in companies. This resulted in the development of a comprehensive catalogue of possible measures for the BDSI members, which can be implemented according to each individual situation. www.lci-koeln.de www.bdsi.de 8/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY Furthermore, both BDSI as well as the LCI are in close contact with other sectors of the food industry, with packaging suppliers of the confectionery industry, and with all other parties involved in the food supply chain since the minimisation of mineral oil components can only be achieved if all stakeholders participate actively. ConCLUSION The ubiquitous presence of mineral oil components, the many possible sources of migration of MOSH and MOAH into foods, the challenging chemical analysis, and the many participants in the food supply chain all form a complex issue. Minimising the migration of these substances into foods is an immense challenge and therefore requires time. Through specific measures such as the switch to fresh fibres, the use of mineral-oil-free printing inks, and/or the introduction of suitable barriers, food manufacturers have been able to optimise many product packaging solutions and hence reduce the migration of mineral oil components during transport and storage. Seeing as much has been undertaken in the past and still a lot is currently being done on a national level, German products perform relatively well in international comparisons. As confirmed by the current research project of the LCI, many raw materials are affected by the migration of MOSH/MOAH. Ultimately, joint international efforts of all stakeholders along the food chain – from the farming sector to the raw materials trade, the transportation sector, the food industry, the packaging industry, food traders, and the printing ink industry, including newspaper publishers – are required to minimise mineral oil components in foods. However – despite the best of efforts – a complete elimination will not be possible. 4/2016 GLOSSARy • Batching oils – formulations used to treat fibres such as jute and sisal to facilitate their processing into bags. •Dressings – corrugated cardboard used to line transport containers in order to control humidity during the transport of raw materials and to prevent spoilage. Dressings are usually manufactured from recycled fibres that contain mineral oils. •Hump – also unresolved complex mixture (UCM) – refers to (gas) chromatograms with very broad signals. This is a typical pattern in the analysis of mineral oil hydrocarbons. Because of the huge amount of compounds, there are no sharp peaks of individual components but rather a multitude of individual signals that appear as a hump. •Mineral oil – collective term for liquid distillation products obtained from mineral raw materials that have a highly-complex mixture of hydrocarbons with chains of 10–50 carbon atoms as well as low levels of sulfur- and nitrogen-containing compounds. •MOAH – mineral oil aromatic hydrocarbons – are primarily hydrocarbons consisting of one to four ring systems, which are up to 97% alkylated. MOAH include a large number of various aromatic compounds and represent the smaller fraction (15–25%) of mineral oil components contained in recycled paper and cardboard. •MOSH – mineral oil saturated hydrocarbons – are saturated paraffinic (i. e., open-chain, branched, and often cyclic) hydrocarbons with low to medium viscosity. They represent the main fraction (75–85%) of the mineral oil components in recycled paper and cardboard. www.lci-koeln.de www.bdsi.de 9/ 11 WPD ScIENTIFIC NEWS SERVICE Modern NUTRITION TODAY 4/2016 address for correspondence •POSH – polyolefin oligomeric saturated hydrocarbons – MOSH-like structures that migrate from polyethylene (PE) or polypropylene (PP) films into foods. These cannot be readily distinguished from MOSH and therefore complicate the analysis. •Unsaponifiables – the sum of those components of an edible vegetable fat or oil that cannot be chemically saponified (hydrolysis of an ester). These include sterols, plant-specific hydrocarbons, alcohols, and impurities from mineral oil hydrocarbons. Dr. Reinhard Matissek Food Chemistry Institute (LCI) of the Association of the German Confectionery Industry (BDSI) Adamsstraße 52–54 51063 Cologne E-mail: [email protected] Bibliography [1]International Energy Agency (IEA) (2016): Oil [4]European Food Safety Authority (EFSA) Panel on [2] Market Report: World Oil Demand. URL: https:// Contaminants in the Food Chain (Contam) (2012): w w w. i e a . o r g / o i l m a r k e t r e p o r t / o m r p u b l i c / Scientific opinion on Mineral Oil Hydrocarbons in (Accessed on June 22, 2016) Food. EFSA Journal (10): 2704 Biedermann M., Fiselier K., Grob K. (2009): Aroma- [5]Schnapka J., Matissek R. (2016): MOSH/MOAH in tic hydrocarbons of mineral origin in foods: Method lebensmitteltechnischen Schmierstoffen. Lebens- for determining the total concentration and first mittelchemie 70: 6–7 results. 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Prof. Dr. Reinhard Matissek (Legally responsible for the content under the German Press Act) Adamsstraße 52-54 · 51063 Köln/Germany Phone: +49 221 623 061 · E-Mail: [email protected] or queries: :relations Gesellschaft für Kommunikation mbH Mörfelder Landstraße 72 · 60598 Frankfurt/Germany Phone: +49 69 963 652-11 · E-Mail: [email protected] Printed with mineral-oil-free printing inks klimaneutral natureOffice.com | DE-077-734899 gedruckt www.lci-koeln.de www.bdsi.de 11/ 11
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