Nanoparticle Migration and Packaging Lifecycle

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1 ILSI Europe Workshop - Brussels Nanoparticle Migration and Packaging Lifecycle Dr. Qasim Chaudhry The Food and Environment Research Agency York, United Kingdom The views expressed in this presentation must not be regarded as those of SCCS, EFSA or the UK Government

2 Nanotechnology Applications Overview of safety issues: migration of nanoparticles and potential consumer safety implications potential environmental implications Current state of knowledge and challenges

3 Lifecycle Assessment Safe product design Safety Issues Consumer Safety Migration of nanoparticles from food packaging to packaged foodstuffs; Toxicological effects of nanoparticles in food Environmental Impacts Raw material production, transportation, handling Product formulation and manufacture Product use End of life treatments - re-use, recycling, disposal

4 Consumer Safety Concerns N a n o p a r t i c l e s Inhalation Skin application Ingestion Lung Skin? Other cells and tissues Gut Scientific evidence indicates that: Nanoparticles may cross cellular barriers, and therefore may reach unintended part of the body; exposure to some insoluble, biopersistent nanoparticles via food may lead to adverse health effects.

5 Nanoparticle Uptake/ Translocation Particles diffusion rate through GI mucus depends on size, charge [1], and surface coatings [2] Translocation of smaller nanoparticles>nanoparticles >larger particles [3,4,5]. Smaller nanoparticles cross the mucus layer faster than the larger ones [6] The rate of uptake is times > in Peyer s Patches, compared with the enterocytes [5] Contradicting results on association between dietary particulates and initiation or exacerbation of gut diseases such as Crohen s or irritable bowel syndrome Translocation of nanoparticles to different organs following oral administration of gold nanoparticles [4], silver nanoparticles [7], magnetic nanoparticles [8]. [1] Szentkuti, 1997), [2] Lai et al., 2007, [3] Desai et al., 1996, [4] Hillyer and Albrecht, 2001, [5] Des Rieux et al., 2006, [6] Hoet et al., 2004, [7] Kim et al., 2008, [8] Kwon et al., 2008.

6 Migration Testing Migration testing is carried out in accordance with the existing EU legislation: Directive 82/711/EEC as amended, and Directive 85/572/EEC as amended, which define the rules and the simulants for migration testing for plastic food contact materials. Migration testing involves exposing materials and articles to food simulants under test conditions that are equivalent to the worst foreseeable conditions of use.

7 Migration of Nanoparticles Two polymer-nanocomposites tested at Fera: Bottles made of multilayered PET - containing nanoclay composite embedded between PET layers No detectable migration of nanoclay from PET. Food containers made of polypropylene-nanosilver composite Very low level of migrating silver (less than the limit of quantification) particulate nature of migrating silver could not be established. In either case, the presence of nanoparticles did not affect the migration of other (non-nano) components.

8 * EFSA (2008) 21st list of substances for food contact materials, Scientific Opinion of the Panel on food contact materials, enzymes, flavourings and processing aids (CEF). The EFSA Journal (2008) , Migration of Nanoparticles Migration of silver nanoparticles (up to 300 nm) reported from polyethylene bags (containing 100 μg /g of PE) to food simulants, which increased with time and temperature (Huang et al., 2011); μg of migrating Ag/ dm2 of the PE after 15 day at 25 C; μg of migrating Ag/ dm2 of the PE after 15 day at 50 C. No migration of TiN reported in PET containers (EFSA, 2008)*. No migration of printed particles from printed ink layer in/through substrates detected. Nano scale pigment particles were found to be bound in polymer matrix of printed ink layer (Personal Communication EuPIA). Rate of migration of (non-nano) substances is 6 times slower in polyamide-nanoclay composites (de Abreu et al., 2010).

9 Migration from Biopolymers Avella et al. (2005) determined migration of Fe, Mg and Si in films made of either potato starch, potato starch polyester blend, or their composites with nanoclay. The study stored vegetables in bags for 10 days at 40oC and measured migration of minerals by AAS. No significant increase in Fe and Mg compared to controls, An increase in Si content mg/kg in the case of nanoclay composites of potato starch and potato starch polyester blend respectively, 13 mg/kg for the same polymers without nanoclay, ~3 mg/kg in unpackaged vegetables Difficult to draw a parallel from migration patterns in plastic polymer composites to biopolymers

10 Modelling Migration Behaviour of Nanopartıcles Diffusion is an important factor that influences migration behaviour of chemical substances (Fick s second law of diffusion); Interactions that may lead to migration in nanocomposites are more complex; Šimon et al. (2008) used a physicochemical perspective to model the factors: migration requires establishment of an equilibrium distribution of nanoparticles between packaging and the packaged food. important variables that can influence nanoparticle migration include time, temperature, and radius of nanoparticle, and dynamic viscosity of polymer.

11 Modelling Migration of Nanoparticles

12 Migration of Nanopartıcles On the basıs of modellıng: any detectable migration of nanopartıcle from packaging to food could take place only in the case of very small nanopartıcles (lower nm range), that are not bound in the polymer matrices which have a relatively low dynamic viscosity (e.g. polyolefines such as LDPE, HDPE, PP) any appreciable migration would be unlikely in the case of nanopartıcles that are larger, bound with polymer matrix, or the polymer has a relatively high dynamic viscosity (e.g. PS and PET)

13 Migration of Nanopartıcles Some assurance from the available migration studies so far that nanoparticles are not likely to migrate in most plastic polymer composites; Some polymer (especially biopolymer) composites may behave differently; More migration studies needed to draw conclusions on potential risk to the consumer. R&D into new materials Assessment of market & economic feasibility Development of new properties/ functionalities Safety studies (e.g. migration testing) Safety must be amongst the first considerations and should drive safe design of new products.

14 Nano-coatings EFSA opinion (2007)* A barrier nano-coating of silicon dioxide formed in situ on the inner surface of PET articles from the monomers - hexamethyldisiloxane and hexamethyldisilazane; According to EFSA opinion overall migration was not determined but given the very low thickness of the coating this information is not required. * EFSA (2007) Opinion of the Scientific Panel on food additives, flavourings, processing aids and materials in

15 Implications of Nanoparticle Migration 1. In case of a significant migration: a. long-term health effects of consumer exposure to nanopartıcles via food are not known; b. any deliberately released nanomaterials will be seen as food additives under the Regulation; 2. In case of a low or no migration: a. surface biocidal effects may only be marginal; b. effects may not last long, especially in the case of re-usable packaging.

16 Environmental Impacts Lifecycle Assessment (LCA) Definition of the scope to describe a product system - boundaries and a functional unit; Data collection to develop life cycle inventory for quantification of various inputs and outputs at different stages of a product system Life Cycle Impact Assessment (LCIA) to evaluate potential environmental impacts. Interpretation, conclusions & recommendations Current Limitations new functionalities/uses of nanocomposites for which there may not be an equivalent non-nano comparison lack of data on a number of parameters* for a like-forlike polymer system with and without nanomaterial * data on physicochemical properties, environmental behaviour and fate and effects of nanomaterials

17 Lifecycle Assessment Only a few examples of LCA for nanocomposites are available so far. Roes et al. (2007) carried out LCA on PP as packaging film, PP as agricultural film, and glass fibre-reinforced PP as automotive panels; LCIA included non-renewable energy use, climate change (Global Warming Potential, GWP100), abiotic depletion, ozone layer depletion, photochemical oxidant formation, acidification, and eutrophication but did not include toxicity or ecotoxicity; LCA showed benefits in terms of reduction of the materials used to achieve the same level of performance (e.g. barrier properties) of PP: 9% for packaging film 36.5% for agricultural film 1.25% for automotive panels.

18 Lifecycle Assessment Manufacturing: Nanoparticle emissions during manufacturing/ formulation stages can be effectively controlled through appropriate engineering measures* Transportation: Nanomaterials or resins are likely to be transported in sealed containers, and hence should not pose a risk of exposure except in case of accidental release; Use: Releases of any significant quantities of nanoparticles are not anticipated under normal use of packaging materials contribution due to surface aberration is currently not known. End of life treatments: Mechanisms will be need to be devised for appropriate end-of-life treatment of nano-packaging materials to minimise emissions during re-use, recycling, and disposal (via incineration, landfill, or direct disposal to the environment) * e.g. DuPont (2007) LCA study on the use of carbon nanotubes to improve mechanical and electrical properties of thermoplastics.

19 Summary Safety aspects Migration of nanoparticles from many plastic polymer based nanocomposite packaging to food may not be significant however, more migration studies are needed for different (bio)polymer matrices; Lifecycle considerations can enable safer design of new packaging materials but data for LCA is currently limited. Challenges methods for detection and characterisation of nanoparticles in polymer and food matrices; data on potential emissions of nanoparticle to the environment at different stages of product lifecycle data on fate, behaviour and effects of nanoparticles appropriate end-of-life treatments for nano-packaging

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