NATIONAL DAIRY RESEARCH INSTITUTE | 19 July to 8 August, 2013 Centre of Advanced Faculty Training in Dairy Processing Migration of Additives from Plastic Packaging Materials into Dairy Products P. Narender Raju’ and Ashish Kumar Singh” ‘Scientist, “Senior Scientist, Dairy Technology Division, National Dairy Research Insitute, Karnal Email pnr.ndri@gmail.com INTRODUCTION Pure resins are rarely processed into final products without the addition of selected compounds, called additives that are incorporated during the process of extrusion and molding of a plastic resin or applied externally on the formed material. Resins without additives are sometimes called as barefoot resins. Compounding is the process of uniformly mixing the additives into the resin, to make a homogenous material. It starts with dry mixing and usually ends with an extruder producing pellets. A blend, by definition, is formed from two or more polymer resins which have been mixed together. Concentrate of additive dispersed in a polymer are termed as master batch. Blending of the master batch with the barefoot resin to achieve the desired additive concentration is called letting down. The number and amount of additives incorporated in a resin vary with resin type and application. The presence of additives in packaging applications raises the question of additive migration. Most additives diffuse within the polymer and often tend to migrate to the surface of the material. When a packaged product is indirect contact with a compounded polymer, there may be a transfer of the additive to the product. Excessive intake of such additives has been shown to be toxic. The present article briefly covers the plastics additives and commonly found migrants in dairy products. ADDITIVES USED IN PLASTICS There are a variety of reasons for the use of additives in a resin including (a) to improve the processing conditions, (b) to improve or increase the resin's stability to oxidation, (c) to obtain better impact resistance, (d) to increase or decrease hardness, (0) to control surface tension, (f) to facilitate extrusion and melting, (g) to control blocking, (h) to reduce cost, and () to increase flame resistance. In general, a number of additives are commonly incorporated into plastics used for packaging applications. However, they may be classified based on their functional property into antioxidants, heat stabilizers, UV stabilizers, antiblocking agents, plasticizers, slip agents, anti-slip agents, lubricants, mould release agents, anti-fogging agents, colourants, anti- static agents, nucleating agents, fillers and reinforcements. Some of the important are briefly described below: Antioxidants Polymeric materials chemically deteriorate during fabrication, processing and storage due to a series of complex chemical oxidation reactions with atmospheric oxygen. The major result is (a) chain scission, which can yield a significant decrease in molecular weight and/or (b) crosslinking, which increases molecular weight and affects flow properties. To prevent the damage to the polymer caused by the oxidative degradation, chemical additives called antioxidants are incorporated into the polymer. Two main types of antioxidants are available commercially, primary and secondary antioxidants. Primary antioxidants work by removing free radical species while secondary antioxidants work by interfering with the formation of free radicals. In packaging, polyethylene (PE), polypropylene (PP) and high impact polystyrene (HIPS) account for the majority of the market for antioxidants. Irganox’™ (phenolic antioxidant), Ingafos™ (phosphate antioxidant), butylated hydroxyl toluene (BHT), a-tocopherol, etc. are commonly used as antioxidants in plastics processing. Heat stabilizers They are used to prevent degradation of polymers when they are exposed to heat especially during processing. For most polymers, oxidation is primary mode of reaction and hence,Innovative approaches in processing and packaging of milk and milk products antioxidants function effectively as heat stabilizers. For a few sensitive polymers such as polyvinyl chloride (PVC), other forms of reactions are important such as dehydrochlorination yielding hydrochloric acid and resulting in formation of double bond in the main polymer chain. This reaction imparts a visible colour to PVC, first yellow, then amber, reddish, brown and finally black. Organometallic compounds, salts derived from lead, cadmium, barium, zinc and tin, epoxides and phosphites are most common heat stabilizers used, UV light stabilizers UV radiation from outdoor light and »-radiation used for sterilization can cause photo-oxidation in PS, PP, PVC and other polymers. High energetic UV photons can be captured by a polymeric chain resulting in the breaking of covalent bonds and production of free radicals. Changes in colour, loss of flexibility and gloss and lower molecular weight are some of the effects that can be produced photo-oxidation. There are three types of UV light stabilizers. Those which absorb the harmful UV radiation and emit harmless radiation of larger wavelength and lower energy (UV absorbers), e.g. hydrobenzophenone, those which bring the excited polymeric chain from a higher level of energy to a stable state by absorbing the energy (UV quenchers), 0.9. organosalts of nickel, and free radical scavengers which accepts free radicals and prevents them from reacting with other polymer molecules, e.g. hindered amine light stabilizers (HALS) Plasticizers These are the substances that are incorporated into a rigid plastic to increase its flexibility, workability and extensibility. By reducing the glass transition temperature (T,) and increasing chain lubricity, they also improve processing and extrusion characteristics, reduce the minimum, required processing temperature, reduce hardness and improve low temperature flexibility. Not all plastics require the use of plasticizer, but for certain plastics, such as PVC, the use of an appropriate plasticizer for the desired end use is essential. Without plasticizer, PVC is a semi- crystalline, brittle polymer that is difficult to process. At lower concentrations the plasticizer helps to reduce processing temperatures and helps to minimize the thermal degradation of the polymer. At higher concentrations, besides improving processing conditions, plasticizer reduces hardness and increases flexibility of the final product. The polar nature of PVC gives it a high affinity for plasticizers and therefore, PVC accounts for more than 80% of the total use of plasticizers. Most plasticizers are liquids at room temperatures and have high boiling points and low vapour pressure, so that they are not easily lost from the plastic during processing. The most common plasticizers are the phthalates and among them diethylhexyl phthalate is the most widely used, For food packaging films, only legally approved plasticizers can be used, Most often, an adipate plasticizer, normally di-(2-ethylhexyl) adipate combined with epoxidized soybean oil is used Colorants Colorants give an opaque appearance that can contribute to light protection of a packaged product and also influence consumers purchasing considerations. Hundreds of different colorants are used in plastics packaging industry. Three major categories of colorants are used in plastics viz, dyes, organic pigments and inorganic pigments. Inorganic pigments are widely used in plastics industry as they are less expensive, more opaque and more stable to high ‘temperatures and have less tendency to migrate. However, most of them are extremely toxic since they are oxides of heavy metals such as chromium, lead, cadmium or nickel PLASTICS AND CHEMICAL MIGRATION Food packaging has the prime function to protect food from contamination unti it is consumed and to help keep the food fresh, but it also fulfils other requirements, such as to convey information about the food stuff and present it in an appealing manner. Plastics are able to fulfil a wide range of functional requirements and offer unparalleled advantages compared to other materials. However, it is also important that the food contact material is inert and does not contaminate the food stuff through migration or transfer of substances used in its manufacture Food may interact with packaging materials and this may change the initial mechanical and barrier properties as well as safety of the product. The interaction may be classified into three phenomena: migration, permeation and sorption. Migration of potentially toxic substances from NATIONAL DAIRY RESEARCH INSTITUTE | 19 July to 8 August, 2013Centre of Advanced Faculty Training in Dairy Processing Packaging material to contact phase is also a major concem in the selection and use of materials for food packaging because of the possible effect upon human health. There are two types of migration viz. global and specific migration. Global migration refers to total transfer i.e. the quantity of all substances migrating from the package into the packaged food while specific migration related to the transfer of one or more identifiable substances that is, a constituent of the packaging material. The main factors that control the migration are: i. Diffusion process of migrants: Migration of chemical substances is a diffusion process subject to both kinetic and thermodynamic control and can be described by diffusion mathematics derived from Fick's Law. The mathematics describe the diffusion process as a function of time, temperature, thickness of the material, amount of chemical in the material, partition coefficient and distribution coefficient. The kinetic dimension of migration dictates how fast the process of migration occurs. The thermodynamic dimension dictates how extensively the transfer of substances will be when migration is finished i.e. when the system is at equilibrium, Cp @2Cp a PX Ge dCs als ae 8 Ge where, D, and Ds are diffusion coefficients (diffusivity) of migrant in the polymer (m? s") and food phases (m’ s"), respectively; Cp and Cs are concentrations of migrants in the polymer and food phase, respectively; x is the space coordinates measured normal to the polymer-food interface (m) and tis the time (s). ii, Composition of packaging material: The packaging material is the source of any chemical migration. The extent of any migration depends on the concentration of the chemical in the packaging. if a substance is not present in a packaging material then it cannot migrate. if a substance is present in the packaging then, other things remaining equal, migration levels will be higher if the concentration in the packaging is increased and vice versa. il, The nature and extent of contact: This depends on the physical properties of the food and the size and shape of the pack. Further, if a chemical that may migrate is located in one layer of the packaging material but is separated from the food by an intervening layer, then this barrier layer may retard or prevent migration from occurring. iv. Nature of the food: If the packaging is not compatible with a given type of food then there can be a strong interaction leading to an accelerated release of chemical substances. Examples are the interaction of fats and oils with certain plastics that leads to swelling of the plastic and leaching of substances from that plastic. v. Temperature of contact: The migration of chemicals is like virtually all chemical and physical processes in that it is accelerated by heat. So migration will occur faster if the temperature is raised vi. The duration of contact: Materials suitable for short duration contact may not be suitable for longer service times. The kinetics of migration is first-order in that the extent of migration increases according to the square-root of the time of contact: M xt". vil, Mobility of the chemicals in the packaging material: The mobility of a chemical in the packaging material depends on the size and shape of the molecule, any interaction it experiences with the material, and the intrinsic resistance to mass transfer that the material presents. It is assumed thal the chemical is compatible with the material. If the chemical is not compatible then it could “bloom” to the surface and give enhanced migration. Permeable materials such as plastics, rubbers and elastomers offer some limited resistance to migration but this can not only ocour from the surface but also from the interior of the material, The resistance to mass transfer depends on structure, density, crystallinity, etc, of the material. NATIONAL DAIRY RESEARCH INSTITUTE | 19 July to 8 August, 2013Innovative approaches in processing and packaging of milk and milk products DETERMINATION OF OVERALL MIGRATION OF CONSTITUENTS OF PLASTICS The Bureau of Indian Standards has laid down standard procedure for determining the overall migration of constituents of plastics materials and articles intended to come in contact with foodstuffs (IS 9845: 1998). The standard is applicable for determination of overall migration of constituents of single or multi-layered heat sealable films, single homogenous non-sealable films, finished containers and closures for sealing as lids in the finished form, preformed or converted form. The determination is to be carried out by using stimulants as given in Table 1 for different foods categorized in Table 2. The maximum extraction value of the material shall not exceed 10 mg/dm? or 60 mg/kg. Table 1. Recommended stimulants for determination of migration in to food stuffs Sr.No. | Stimulant Description 1 ‘A__| Distiled water or water of equivalent quality 2 B__| Sper cent acetic acid (w/v) in aqueous solution (using stimulant A) 3 c 710 per cent ethanol (viv) in aqueous solution for food stuffs having alcohol less than 10 per cent (viv) (using the stimulant ‘A’ 4 Cc 50 per cent ethanol (viv) in aqueous solution for food stuffs having alcohol more than 50 per cent (viv) (using the stimulant ‘A’) 5 D__| mheptane (freshly distilled) 6 E*___ | Rectified olive oil or mixture of synthetic triglycerides or sun flower oll *"Slmulant © suggested by EEC for fatly foods fe nat considered al present as the methodology of estimation isnot yet developed. Table 2. Stimulating solvents for different food products Sr.No. | Type Description Examples ‘Stimulants 1 |_| Aqueous, non-acidic Honey, mineral water, skimmed A foods (pH > 5) without fat_| milk, rasogolla, murabba, yeast paste, ote, 2 1 Aqueous, non-acidic Fruit juices, squashes, jams, 8 foods (pH < 5) without fat | jelies, carbonated beverages, sauces, RTS beverages, soups, lemonade, vinegar, etc. 3 Ti _ | Alcoholic beverages: i. Alcohol concentration | Beer and some pharmaceutical c less than 10 per cent | syrups ii, Alcohol concentration | Wine, brandy, whiskey, arrack ce above 10 per cent and other alcoholic drinks a TV] Oils, fats and processed | Vegetable oils, ghee, vanaspati, D dry foods with surface fat | cocoa butter, lard, spice powder, oF Volatile oil snacks and savoury, chocolate, caramels, malted foods, egg powder, fried and roasted nuts, tea, coffee powder, etc. 5 V_ | Non-acidic foods (pH>5) | Butter, bread, pastry, cakes, ‘Rand D ‘or high fat and having —_| shrikhand, milk-based sweets, high moisture content —_| ice-cream, moist and fatty confectionery products 6 Vi_| Acidic foods (pH<5)or | Pickles, ketchup, cheese, curd, | BS andD high fat and having high | fresh and processed meat and moisture content fish products, sauces having fat, frozen foods, mayonnaise, etc. 7 Vil_| Dry processed foods Cereals and pulses, dehydrated | No end test without fat vegetable and fruits, dried yeast, com flakes, salt, sugar, milled products, barley powder, oats, vermicelli, spaghetti, ete, NATIONAL DAIRY RESEARCH INSTITUTE | 19 July to 8 August, 2013NATIONAL DAIRY RESEARCH INSTITUTE | 19 July to 8 August, 2013 & Centre of Advanced Faculty Training in Dairy Processing MIGRATION OF ADDITIVES INTO DAIRY PRODUCTS PVC films are commonly used as “cling” films for wrapping fresh fruits, vegetables, poultry meat, red meat and cheeses at retail level. As mentioned earlier, PVC is almost always processed with plasticizers such as adipates and pthalates. Goulas et al. (2000) studied the migration of d-(2-ethylhexy) adipate (DEHA) plasticizer from food grade polyvinyl chlorde film used to wrap three different types of cheeses (Kefalotyri, Edam and Fela), It was reported that after 240 h of contact, under refrigeration, the migration of DEHA was approximately 345.4 mg/kg (189 mg/dm) for Kefalotyri, 222.5 mg/kg (12.2 mg/dm?) for Edam and 133.9 mg/kg (7.3 mg/dm’) for Feta indicating that the loss of DEHA from the PVC film into the three cheese types was 37.8, 24.3 and 14.6 per cent, respectively. ‘The migration kinetics of diphenylbutadiene (OPBD) from low density poly ethylene (LDPE) film (444 um) into whole milk powder (WMP), skim milk powder (SMP), toast with fat, wheat flour, honey and rice was studied by Silva et al. (2009). It was reported that migration of DPBD was highest in WMP followed by toast with fat, flour and rice and it was negligible in honey and SMP. It was concluded that fat content greatly affects the migration of DPBD in dry foods. CONCLUSION ‘Although all the plastic resins do not require additives for processing into packaging materials, additives aid in improving processability, functional properties and also aesthetics. Dairy products depending on their composition and intended shelf life interact with packaging materials differently. Hence, there is a need to choose appropriate packaging material so that the overall migration of migrants would be within the limits prescribed. SUGGESTED READINGS 1S 9845 (1998). Determination of the overall migration of constituents of plastics materials and articles Intended to come in contact with foodstuffs-method of analysis. Bureau of Indian Standards, New Delhi Goulas, A.E., Anifantaki, K.l,, Koliouis, D.G, and Kontominas, M.G, (2000), Migration of di-(2-ethythexyl) acipate plasticizer from food grade polyvinyl chloride film into hard and soft cheeses. Journal of Dairy Soience, 83: 1712-1718, Siva, AS., Freire, J.M.C., Sendon, R., Franz, R. and Losada, P.P. (2009). Migration and diffusion of diphenylbutadiene from packages into foods. Journal of Agriculture and Food Chemistry, 87:10225- 10230.