PACKAGING TECHNOLOGY AND SCIENCE Packag. Technol. Sci.

2011; 24: 291–297 Published online 14 April 2011 in Wiley Online Library (wileyonlinelibrary.com) DOI: 10.1002/pts.938

Nanosilver Migrated into Food‐Simulating Solutions from Commercially Available Food Fresh Containers
By Yanmin Huang,1,2 Shuxiang Chen,1,3* Xin Bing,1 Cuiling Gao,1,3 Tian Wang1 and Bo Yuan1
Shandong Key Laboratory for Testing Technology of Material Chemical Safety, East Jingshi Road 8168, Jinan 250103, China 2 School of Chemistry and Chemical Engineering, Shandong University, Jingshi Road 17923, Jinan 250061, China 3 National Packaging Products Quality Supervision and Inspection Center (Jinan), East Jingshi Road 8168, Jinan 250103, China
1

Manufacturers of food fresh containers use nanosilver as an antimicrobial agent, but the safe impacts of nanosilver release from commercial products are unknown. The nanoparticles that migrate from the consumer products should be determined to assess the safety and/or risks of nanotechnology. This paper describes experimental work carried out on one kind of commercial food fresh container (polyethylene plastic bags). In the experiments, the range of temperatures was from room temperature (about 25°C) to 50°C, the range of time intervals was from 3 to 15 days, and the bags were filled with four kinds of food‐simulating solutions representing water, acid, alcohol and fatty foods, respectively. Microwave digestion method was used for sample pre‐treatment. The scanning electron microscopy and energy‐dispersive X‐ray (SEM/EDX) analysis was used to confirm the presence and morphology of nanosilver additives, and the atomic absorption spectroscopy (AAS) analysis was applied, showing that the commercial bags contained 100 μg (Ag)/g (plastic materials). Strong evidences from SEM/EDX and AAS analyses were found, indicating the migration of nanosilver from the polyethylene bags into food‐simulating solutions. The amount of nanosilver migration was observed as increasing with storage time and temperature. Copyright © 2011 John Wiley & Sons, Ltd.
Received 29 December 2009; Revised 8 December 2010; Accepted 17 January 2011 KEY WORDS: nanosilver; plastics; migration; food safety; polyethylene

INTRODUCTION In recent years, nanomaterials have attracted increasing attention because of their potential application in a wide range of industries and markets. Until now, the Project on Emerging Nanotechnologies at Woodrow Wilson International Center for Scholars has compiled a list of more than 1000 consumer products that claim to include some form of engineered nanoparticles.1 Of these products, about 24% contain nanosilver. Manufacturers of plastic food containers incorporate nanosilver to exploit its antimicrobial properties by restricting the growth of bacteria,2–6 because of its small dimension, quanta and large external area effect, which give nanosilver more effective antibacterial activity than the normal‐sized silver particles.7 As commercialization of nanosilver grows, the public and the governments become more and more concerned about the safety and environmental effects of the widespread use of products containing nanosilver.8 Studies have been carried out, and they demonstrated the toxicity of nanosilver, which is proved to be hazardous to safety and the environment. For example, Hussain et al.9 studied the

* Correspondence to: S. Chen, National Packaging Products Quality Supervision and Inspection Center (Jinan), East Jingshi Road 8168, Jinan 250103, China. E-mail: kedachenshuxiang@yahoo.com.cn Copyright © 2011 John Wiley & Sons, Ltd.

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toxicity of nanosilver with different size dimensions on rat liver. The authors found that after an exposure for 24 h, the mitochondrial cells displayed abnormal size, cellular shrinkage and irregular shape. Cytotoxicity study of five nanosilvers impregnated with commercially available dressings was undertaken by Burd et al.10. In their study, it was found that three of the silver dressings depicted cytotoxicity effects in keratinocytes and fibroblast cultures. Braydich‐Stolle et al.11 reported the toxicity of nanosilver on C18‐4 cell, a cell line with spermatogonial stem cell characteristics. From their studies, it was concluded that the toxicity of nanosilver to the mitochondrial activity increased with the increase in the concentration of nanosilver, and nanoparticles are more likely to intrude cells than normal‐sized particles do. In the last few years, the food contact materials with nanosilver have been widely used. The ubiquitous use of commercial products containing nanosilver may potentially compromise the health of many organisms, because food contact materials containing nanosilver may release silver nanoparticles into foods. It is important to study the migration of nanosilver from commercial products to foods; however, it is ignored whether nanosilver can migrate into food from nanomaterials and the potential hazard after nanosilver migrated into food. The migration of nanosilver from food contact materials has never been reported until recently;12–14 a theoretical research has been carried out from a physicochemical view, of which the results indicated that the migration of nanoparticles from packaging to food will be detected only in the case of very small particles within the radius of 1 nm from the polymer matrices, and for bigger nanoparticles, the migration will not be detectable.15 This paper aimed to investigate the migration of nanosilver from a commercially available kind of polyethylene plastic food fresh bag into food‐simulating solutions, as well as the quantity and the morphology of the migrated nanosilver. The amount of nanosilver in the food fresh bag was quantified before the experimental work of migration was carried out.

MATERIALS AND METHODS Microwave digestion of nanosilver plastic Commercially available nanosilver food fresh bag made of polyethylene plastic (Sunriver Industrial Co., Ltd, Quanzhou, Fujian, China) was used as the original material. The bag is 0.07 mm thick, and its density is 1.3 g/cm3. A microwave digestion method was used to quantify the total amount of silver in the fresh bags. A precise mass of 0.2 g chopped nanosilver plastic pieces was submerged in a digestion tube within a mixed solution of 5 ml of nitric acid and 2 ml of hydrogen peroxide. Then the tube was put into the microwave digestion oven (CEM MARS, Matthews, NC, USA). The experiments indicated that the sample could get better digestion under the optimized microwave procedure (Table 1). After the microwave procedure, the digestion solution was cooled, filtered through a glass fibre filter and diluted to 50 ml. Silver was quantified by atomic absorption spectroscopy (AAS, ICE 3000 Series, Thermo Scientific, Franklin, MA, USA). Migration experiments The bags were of 15 × 15 cm each in dimension, and the method of single surface testing by filling was chosen in this study according to the properties of the materials. The food‐simulating solutions selected for the study were of the following quality: simulating solution A (ultrapure water),

Table 1. Optimized microwave digestion procedure. Power Stage
1 2

Maximum power (W)
1200 1200

Utilization rate (%)
100 100

Temperature rise time (min)
6 7

Controlled temperature (°C)
120 190

Holding time (min)
1 30

Copyright © 2011 John Wiley & Sons, Ltd.

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simulating solution B [4% acetic acid (v/v)], simulating solution C [95% ethanol (v/v)] and simulating solution D (hexane). The simulating solution A (ultrapure water), simulating solution B [4% acetic acid (v/v)] and simulating solution D (hexane) are official food simulants according to the Chinese standard GB/T 5009.60‐2003, representing water, acid and fatty foods, respectively. The simulating solution C [95% ethanol (v/v)] was used as a high‐level solution of ethanol simulant, which leads to an increase in the migration levels and therefore represent a worst‐case scenario for migration testing. Bags were washed with ultrapure water and dried in the air before being used as testing materials; then each bag was filled with 200 ml of simulating solution and sealed in a clean wide‐mouth bottle for storage, and the prepared samples were stored at room temperature and in ovens at temperatures of 40°C and 50°C. The total migration time was 15 days. The aforementioned stored temperature and time for the experiments were chosen based on the possible circumstances of the actual and worse cases for use, which would be beneficial to study the migration laws. The 200 ml of sample solutions collected at intervals of 3, 6, 9, 12 and 15 days from the aforementioned storages was concentrated to dry, redissolved in 10 ml of ultrapure water with 5 ml of 50% nitric acid (v/v) by ultrasonator, then diluted to 50 ml and analysed for the silver migration quantity by AAS. Scanning electron microscopy/energy‐dispersive X‐ray analysis Scanning electron microscopy [Hitachi S‐4800 with energy‐dispersive X‐ray (EDX) capabilities, Hitachi, Tokyo, Japan] was used to test the presence and the morphology of nanosilver in the fresh bag material and in the migration substances. The fresh bag material was turned into ash under 600°C to obtain some original powder of the plastics. The four kinds of food‐simulating solutions were, respectively, collected and concentrated to obtain migration substances, in which there was not only nanosilver but also some other additives (e.g. antioxidant, plasticizer, colouring agent, impact modifier) that migrated from the plastic materials. The ash and the concentrated migration substances were then dispersed in some alcohol solution and subsequently evaporated in droplets onto the aluminium foil of the scanning electron microscopy (SEM) stub for the morphology study. EDX was used to confirm the presence of nanosilver in the electron micrographs.

RESULTS AND DISCUSSION Test of nanosilver in fresh bag plastic The AAS analysis of the microwave‐digested solution indicated that the fresh bag plastic material contained silver with an average level of 0.4 μg/ml in a 50 ml solution; thus, the total quantity of silver was 100 μg (Ag)/g (plastic materials). SEM/EDX analysis results confirmed the presence of nanosilver in the polyethylene plastics and revealed the morphologic properties of the nanosilver additives. Figure 1a shows the SEM image of the ash, in which there were many spherical nanoparticles with a range from 100 to 300 nm. Figure 1b shows a representative EDX analysis of points within the spherical nanoparticles and confirms a majority of nanosilver. The aluminium peak of EDX analysis could be attributed to the aluminium foil used for SEM stub preparation, whereas the carbon and oxygen peaks could be attributed to the surrounding residual additives and spray carbon treatment for observing SEM pictures of the sample. Characterization of nanosilver in the migration substances SEM/EDX analysis confirmed the presence of nanosilver in the migration substances from the simulating solutions. Figure 2 shows SEM/EDX images of a representative sample of migration substance from water under 50°C and 15 days. As the reaction between silver particles and water under the aforementioned experimental condition is unlikely, the silver that migrated into water was presented in a particle state. The SEM image demonstrated the migrated silver in the form of
Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2011; 24: 291–297 DOI: 10.1002/pts

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(a)

(b)

Figure 1. (a) SEM image of the ash of plastics showing original nanosilver particles, ranging from 100 to 300 nm in diameter. (b) Representative EDX analysis of points within the spherical nanoparticles confirms a majority of silver particles. spherical particles within 300 nm in diameter. The EDX image confirmed a majority of nanosilver in the micro‐areas. The aluminium peak of EDX analysis could be attributed to the aluminium foil used for SEM stub preparation, whereas the carbon and oxygen peaks could be attributed to the surrounding residual additives and spray carbon treatment for observing SEM of the ash. The results indicated that the nanosilver added in the polyethylene plastic migrated into the food‐ simulating solutions, and the migrated particles were within 300 nm in a nanosize dimension, which was already demonstrated harm to the safety of an organism.9–11 Migration amount of silver into simulating solutions According to the analysis of AAS, the plastic materials of commercial food fresh bags detectably released silver into the four kinds of food‐simulating solutions. Figure 3 presents the total amount of silver that migrated from one bag into each kind of simulating solutions at different temperatures and time intervals. The amount of silver migration is observed as increasing with storage time and temperature. The following considerations give a hint to the migration process taking place. The initial release of
Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2011; 24: 291–297 DOI: 10.1002/pts

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(a)

(b)

Figure 2. (a) SEM image of migration substance from simulating solution of water under 50°C and 15 days, showing spherical silver particles within 300 nm in diameter. (b) EDX result of the particles confirms a majority of nanosilver. nanosilver must be from those silver particles, which are encapsulated within the surface layers of the specimen. The subsequent release of nanosilver from the interior part of the specimen has to cross the diffusion barrier, which could be constituted by many crystalline lamellae.16 In plastics, the water and organic molecules in the interlamellar regions can change the overall crystalline state.17 The onset of plasticization followed by the equilibrium sorption could provide substantial mobility to the macromolecular chains especially within the amorphous regions and some favourable changes in the crystalline regions as well. The nanosilver particles encapsulated well inside the specimen need to oxidize and migrate out through the polyethylene specimen. These silver particles are predominately responsible for the release at later times. According to the dual sorption theory,18 there are two different physical mechanisms that affect mass transfer: diffusion and embedding (intermolecular forces between the penetrant molecules and the polyethylene specimen). However, the diffusion process is faster than the embedding process. The water and organic molecules, initially embedding the polymeric specimen, will ultimately plasticize and widen the interspace between the polymer chains. So the widening of the chains facilitates the nanosilver migration through the equilibrated specimen.
Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2011; 24: 291–297 DOI: 10.1002/pts

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Figure 3. The amount of migrated silver/dm2 of bag into simulating solutions with temperature and time. (a–d) Solutions A–D. CONCLUSIONS Results obtained in this study indicated that nanosilver could migrate from one kind of commercial available food contact plastic bag into food‐simulating solutions representing water, acid, alcohol and fatty foods. The migration size of nanosilver is less than 300 nm, which is a hazardous dimension to the safety of organisms. The amount of nanosilver migration was observed as increasing with storage time and temperature. The potential risks of nanosilver are currently preventing scientists and the public from fully supporting the advancement of nanosilver technology that should develop at a pace acceptable to people’s safety.

ACKNOWLEDGEMENTS
The authors acknowledge the financial support of the Science & Research Program of the General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China.

REFERENCES
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3. Morones JR, Elechiguerra JL, Camacho A et al. The bactericidal effect of silver nanoparticles. Nanotechnology 2005; 16: 2346–2353. 4. Panacek A, Kvitek L, Prucek R et al. Silver colloid nanoparticles: synthesis, characterization, and their antibacterial activity. The Journal of Physical Chemistry B 2006; 110: 16248–16253. 5. Sondi I, Salopek‐Sondi B. Silver nanoparticles as antimicrobial agent: a case study on E‐coli as a model for Gram‐negative bacteria. Journal of Colloid and Interface Science 2004; 275: 177–182. 6. Yoon KY, Byeon JH, Park JH, Hwang J. Susceptibility constants of Escherichia coli and Bacillus subtilis to silver and copper nanoparticles. The Science of the Total Environment 2007; 373: 572–575. 7. Li HM, Li F, Wang L et al. Effect of nano‐packing on preservation quality of Chinese jujube. Food Chemistry 2009; 114: 547–552. 8. Morris J, Willis J. U.S. Environmental Protection Agency Nanotechnology White Paper; U.S. Environmental Protection Agency: Washington, D.C., 2007. 9. Hussain S, Hess K, Gearhart J, Geiss K, Schlager J. In vitro toxicity of nanoparticles in BRL3A rat liver cells. Toxicology in Vitro 2005; 19: 975–983. 10. Burd A, Kwok CH, Hung SC et al. A comparative study of the cytotoxicity of silver‐based dressings in monolayer cell, tissue explant, and animal models. Wound Repair and Regeneration 2007; 15: 94–104. 11. Braydich‐Stolle L, Hussain S, Schlager J, Hofmann MC. In vitro cytotoxicity of nanoparticles in mammalian germ line stem cells. Toxicological Sciences 2005; 88: 412–419. 12. Environmental, Health, and Safety Research Needs for Engineered Nanoscale Materials. National Nanotechnology Coordination Office (NNCO), Arlington, VA, September 2006. 13. Davies JC. EPA and Nanotechnology: Oversight for the 21st Century. Woodrow Wilson International Center for Scholars: Washington, D.C., 2007. 14. Karn B, Roco M, Masciangioli T, Savage N. Nanotechnology and the Environment: Report of a National Nanotechnology Initiative Workshop. National Science and Technology Council, Committee on Technology, and Subcommittee on Nanoscale Science, Engineering, and Technology, Arlington, VA, 8–9 May 2003. 15. Šimon P, Chaudhry Q, Bakoš D. Migration of engineered nanoparticles from polymer packaging to food – a physicochemical view. Journal of Food and Nutrition Research 2008; 47: 105–113. 16. Murthy NS, Stamm M, Sibilia JP, Krimm S. Structure changes accompanying hydration in nylon 6. Macromolecules 1989; 22: 1261–1265. 17. Alt V, Bechert T, Steinrucke P et al. An in vitro assessment of the antibacterial properties and cytotoxicity of nanoparticulate silver bone cement. Biomaterials 2004; 25(18): 4383–4391. 18. Mi FL, Wu YB, Shyu ACA, Lai J, Su C. A symmetric chitosan membranes prepared by dry/wet phase separation: a new type of wound dressing for controlled antibacterial release. Journal of Membrane Science 2003; 212: 237–254.

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Packag. Technol. Sci. 2011; 24: 291–297 DOI: 10.1002/pts

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