Accepted Manuscript

Safety assessment of nanocomposite for food packaging application

Jen-Yi Huang, Xu Li, Weibiao Zhou

PII:

S0924-2244(15)00169-7

DOI:

10.1016/j.tifs.2015.07.002

Reference:

TIFS 1681

To appear in:

Trends in Food Science & Technology

Received Date: 9 December 2014

Revised Date:

1 July 2015

Accepted Date: 4 July 2015

Please cite this article as: Huang, J.-Y., Li, X., Zhou, W., Safety assessment of nanocomposite for food
packaging application, Trends in Food Science & Technology (2015), doi: 10.1016/j.tifs.2015.07.002.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
37
38
39
40
41
42
43
44
45

Safety assessment of nanocomposite for food packaging application

Huang, Jen-Yi a, Li, Xu b and Zhou, Weibiao a, b, c, *
a

Food Science and Technology Programme, c/o Department of Chemistry, National

University of Singapore, 3 Science Drive 3, Singapore 117543
b
Institute of Materials Research and Engineering, Agency for Science, Technology
and Research, 3 Research Link, Singapore 117602
National University of Singapore (Suzhou) Research Institute, 377 Linquan Street,
Suzhou Industrial Park, Jiangsu, 215123, Peoples Republic of China
*Corresponding author; e-mail: chmzwb@nus.edu.sg, tel.: +65 6516 3501, FAX:

RI
PT

36

+65 6775 7895

48
49

Abstract
While competition is intense and innovation is vital in the domain of

50
51
52

nanotechnology, utilisation of nanocomposites in food packaging has become the

most developed area in the food industry. Migration of nanocomponents from
nanocomposite packaging contacting with foodstuffs, is one of the most important

53
54
55
56

concerns in human exposure to nanomaterials and therefore potential health risks.

Risk assessment of nano-packaging materials provides an unique challenge for food
safety. This article explores the current efforts on migration assessment for
nanocomposites in food packaging, and provides a better understanding of the

57
58
59
60

existing relevant regulatory setups for protecting public health.

M
AN
U

TE
D

EP

62

Keywords: nanomaterial; migration; food packaging; safety assessment; regulatory

framework

AC
C

61

SC

46
47

ACCEPTED MANUSCRIPT
63

1.

Introduction
Nanotechnology is by definition the manipulation and utilisation of structures with

65

at least one dimension in the nanometre-length (atomic, molecular, macromolecular)

66

scale, which creates unique properties and functions for novel applications.

67

Nanomaterials can occur naturally (e.g. in ashes, as soil particles or biomolecules), be

68

produced unintentionally (e.g. in diesel exhaust) or be intentionally engineered (Tiede

69

et al. 2008). Nano-food packaging is a new generation of packaging technology based

70

on nanomaterials, which has become one of the most developed areas in

71

nanotechnology and represents a radical alternative to the conventional food

72

packaging. Fillers are entities incorporating into traditional packaging materials,

73

mostly in low fractions, to improve the properties of the original material (Cushen et

74

al. 2014b). Reinforcement by engineered or natural nanomaterials as fillers, has

75

appeared to be an interesting strategy for improving the functional properties of

76

synthetic and biosourced materials. Two main approaches are used to produce

77

nanomaterials. In the top-down approach, nanometric structures are obtained by

78

size reduction of bulk materials, involving grinding, chemical and laser abrasion. The

79

alternative bottom-up approach, allows nanostructures to be built from individual

80

atoms or molecules capable of self-assembling, involving a metal salt that is reduced

81

with a reducing agent to reveal the metal in the nanoform.

SC

M
AN
U

TE
D

EP

AC
C

82

RI
PT

64

Polymer nanocomposites can potentially be used as food packaging materials, and

83

can be categorised into four types based on the purpose of use (Chaudhry et al. 2008):

84

(1) Improved packaging: polymers with nanofillers, i.e. polymer nanocomposite,

85

aiming at improving the packaging properties, such as barrier properties against

86

oxygen, carbon dioxide, volatiles and flavour, temperature control, moisture stability

87

and ultraviolet blocking properties, have received much attention due to the potential

88

to increase the shelf life of fresh and processed food which are packed under modified
2

ACCEPTED MANUSCRIPT
atmosphere. Polymer nanocomposite can improve the quality of fresh, frozen, and

90

processed meat, poultry, and seafood products by retarding moisture loss, reducing

91

lipid oxidation and discolouration, and enhancing product appearance.

92

(2) Active packaging: incorporation of nanofillers with antimicrobial or antioxidant

93

activities (e.g. silver, zinc oxide, magnesium oxide), which results in an inhibiting or

94

retarding effect on the targeted accelerating factors of microbial growth and food

95

spoilage. These active packaging systems can extend the products shelf life, enhance

96

food quality and safety and ultimately lead to less food waste (Cushen et al. 2012).

97

(3) Intelligent packaging: incorporation of nanosensors into food packaging materials

98

improves detection and tracking of the food condition during storage and transport for

99

safety and biosecurity purposes. It communicates information to the consumer based

100

on its ability to monitor, trace, or record external or internal changes in the products

101

environment.

102

(4) Degradable or compostable biopolymers: biopolymers are notorious for their low

103

mechanical strength, poor gas barrier properties, reduced thermal stability and low

104

melt viscosity. The incorporation of nanofillers, resulting in biopolymer

105

nanocomposite materials, has risen as a solution to these problems is to improve the

106

chemical and physical properties of the biopolymer. Biopolymer nanocomposites can

107

be used to extend the shelf-life of the fresh products such as fruits and vegetables by

108

controlling of respiratory exchange (Akbari et al. 2007).

SC

M
AN
U

TE
D

EP

AC
C

109

RI
PT

89

As commercialisation of nanotechnologies grows, the public and the governments

110

become more concerned about the safety effects of the widespread use of

111

nanocomposites as food packaging materials, such as whether nanomaterials can

112

migrate towards the packaged foodstuffs and drinks from packaging as well as the

113

potential hazard consumer health after nanomaterials migrated (Huang et al. 2011).

114

The reason for this status is that properties of materials at nano-size can be
3

ACCEPTED MANUSCRIPT
substantially different from conventional bulk forms as well as individual molecules,

116

and their toxicity is not yet completely understood. Due to limited toxicity data

117

available, some nanomaterials are not approved in the European Union (EU) (Cushen

118

et al. 2014a). In addition to the physicochemical and biological nature, toxicity can be

119

dependent on the particle size, morphology, and surface behaviours of the

120

nanomaterials (Magnuson et al. 2011). The consumer safety implications from

121

nanotechnology applications in food are intrinsically linked to the likelihood and

122

extent of exposure through its consumption. Most consumers are concerned about the

123

application of nano-containing food packaging materials before its safety is verified

124

by appropriate and

125

Nanomaterials that have been proved to migrate in insignificant levels or not to

126

migrate are approved (EFSA 2012). Therefore, quantifying human exposures to

127

nanoparticles migrating from packaging materials is an important procedure to

128

determine the risk from an increased use of nanomaterials (Cushen et al. 2014b).

testing and

exposure assessment.

TE
D

M
AN
U

accurate migration

SC

RI
PT

115

Migration tests are important for the food packaging sector, and must therefore be

130

performed during the introduction process of a nano-packaging material (Cushen et al.

131

2013). Approval for the application of a new food packaging material depends on its

132

migration assessment. However, limited empirical data are currently available on the

133

potential migration of nanomaterials from manufactured products and their

134

subsequent effect on foodstuff, although numerous nanotechnology-derived food

135

packaging materials are commercially available in several countries (Song et al. 2011).

136

Once the test results are available, potential human exposure assessments are a logical

137

progression based on migration data, especially in the case of migration into real

138

foodstuffs (Cushen et al. 2014a). Thorough exposure assessment of nanotechnology

139

application in the food packaging could enhance consumers knowledge about the

140

risks of migration. A sound foundation should be provided on which products can be

AC
C

EP

129

ACCEPTED MANUSCRIPT
141

commercialised with confidence, or withdrawn to prevent consumers from potential

142

hazards.
The rest of this article presents a comprehensive review of the latest migration

144

assessments of nanomaterials from food packaging. It starts with an introduction of

145

various nanomaterials recently implemented into food packaging. Furthermore, an

146

overview of the different analytical techniques available for identification,

147

characterisation and quantification of nanomaterials in food is provided. It then

148

highlights some recent results of migration tests for nanocomposite packaging. The

149

last part of this article is to summarise the current regulatory frameworks in various

150

judiciaries for new nano-sized components in both food matrix and contact materials

151

focusing on the safety aspects. Since relatively little work has been reported to date,

152

this review is beneficial to develop appropriate migration study protocols for

153

addressing nanomaterials used in food packaging.

M
AN
U

SC

RI
PT

143

155

2.

TE
D

154

Nanomatarials in food packaging

Because of the unique physical and chemical properties of nanomaterials, various

157

inorganic nanomaterials have been recognised as possible additives to polymers to

158

enhance their performance. By bottom-up approach, nanomaterials can provide

159

multifunctional activity. Reinforcing nanofillers are useful for various applications,

160

including clay and silicate nanoplatelets, silica nanoparticles, carbon nanotubes and

161

graphene (Duncan 2011). There is abundant evidence to build the benefits of

162

inorganic nanofiller on food packaging materials, among which there are enhanced

163

maintenance of flavour, colour and texture, improved stability during storage and

164

transport, decreased spoilage and better appearance (Sorrentino et al. 2007). Metal

165

and metal oxide nanomaterials have received much attention in antimicrobial active

166

food packaging. Their successful application depends upon controlled synthesis. The

AC
C

EP

156

ACCEPTED MANUSCRIPT
solution-phase techniques allow high consistency among products (de Azeredo 2013).

168

Metal oxides have also been incorporated into commercialised products displaying

169

light activated microbe inactivation. Packaging materials containing metal

170

nanoparticles have been commercially available outside the EU for many years, e.g.

171

nano-Ag embedded baby bottles (Cushen et al. 2012), nano-ZnO based films for

172

wrapping foodstuffs (Top Nano Technology, Taipei, Taiwan).

RI
PT

167

This section summarises the development of the new nano-sized components that

174

have been used and proposed in the research literature and scientific reports as

175

applicable to food packaging strategies. Table 1 is a summary of the latest

176

implementation of engineered nanomaterials into food packaging systems, and the

177

findings on their actual performance.

M
AN
U

SC

173

178
179

2.1. Clay

Polymer incorporated with nanoclay is one of the first polymer nanocomposites to

181

appear on the market as a novel material for food packaging. Nanoclays are the widest

182

commercial application of nanoparticles and constitute almost 70% of the market

183

volume (Silvestre et al. 2011). This is not only due to the availability and low cost of

184

clay but also their significant enhancements, relatively simple processability, high

185

stability and benignity (Sorrentino et al. 2007). The most common clay nanoparticle

186

utilised in these nanocomposites is montmorillonite (MMT), which is a type of

187

comprehensively available natural clay mineral originated from rocks or volcanic ash.

188

MMT clays belong to the structural family of the 2:1 layered phyllosilicates or

189

smectites, consisting of a layer of edge-shared aluminum or magnesium hydroxide

190

octahedral locating between two silicon oxide tetrahedral layers. Their dimensions, 1

191

nm thick and 100 to 500 nm in lateral extension, result in platelets with high aspect

192

ratio (i.e. the largest to the smallest dimension) of 100 to 500. Clay structure is formed

AC
C

EP

TE
D

180

ACCEPTED MANUSCRIPT
by hundreds of negatively charged silicate sheet layers periodically stacked into

194

particles or tactoids of 8 to 10 mm in diameter (Rodriguez et al. 2013). The imbalance

195

of the surface negative charges is due to isomorphous substitution of Si4+ for Al3+ or

196

Al3+ for Mg2+ within the silicate layers and it is compensated by exchangeable cations

197

(typically Na+ and Ca2+) occupying the space of the interstitial layers (Sorrentino et al.

198

2007). The formation of the layer into stacks is separated by a regular van der Waals

199

gap, which is called the interlayer or gallery (~1.26 nm) and allows for the multi-layer

200

polymer assemblies to be constructed at appropriate conditions.

SC

RI
PT

193

A nanocomposite can be exfoliated or intercalated, which depends on the

202

exfoliation degree of nanoparticles in polymeric matrices. If the nanoparticles are

203

fully dispersed between the polymeric matrices, the nanocomposite is exfoliated (de

204

Abreu et al. 2010). Nanoclay has a natural nano-scaled layer structure, which however,

205

come in platelet clusters with little surface exposed. Therefore, they should be

206

exfoliated as individual platelets and homogeneously dispersed within the polymer

207

matrix in order to take full advantage of the potentially high surface area, in excess of

208

750 m2 g1.

TE
D

M
AN
U

201

When dispersed into polymers, nanoclays inherently resist the permeation of gases

210

or other substances, and provide substantial improvements in barrier properties of the

211

nanocomposite. The enhanced barrier performance of clay/polymer nanocomposites

212

are widely explained on the basis of a maze structure created by impermeable clay

213

plates, forcing the penetrating molecules to travel a longer tortuous path to diffuse

214

through the film. The increase in path length is a function of the aspect ratio of the

215

clay filler, their volume fraction, degree of dispersion and orientation in the composite.

216

The packaging materials incorporating exfoliated nanoparticles exhibit higher barrier

217

performance than that with intercalated nanoparticles (de Abreu et al. 2010).

218

Nanoclays embedded in food packaging films decrease gas transmission rate in order

AC
C

EP

209

ACCEPTED MANUSCRIPT
219

to keep the freshness of oxygen-sensitive foods and prolong their shelf life. A few

220

Breweries have been reported to be already using the technology in their beer bottles.

221

The storage time of beer increases from 11 to 30 weeks when nanoclay is

222

incorporated in the bottles (Silvestre et al. 2011).

Besides the substantial improvements in gas barrier properties of polymer

224

composites, nanoparticles can be utilised as carrier of antibacterial agents and

225

additives. Some studies have reported the increased tortuosity effect of dispersed

226

nanoclays on stabilising additives and efficiently prolonging retention or controlling

227

transfer of antibacterial agents by polymer matrices (Chakraborti et al. 2012; Girdthep

228

et al. 2014). A controlled release from packaging film to the food surface has many

229

benefits compared to spraying and dipping. This control can be especially important

230

for long-term storage of foods or for imparting specific desirable characteristics, such

231

as flavour, to a food system. As a consequence of this, such systems are very

232

promising in the active packaging field (Sorrentino et al. 2007).

233
234

2.2. Silver

TE
D

M
AN
U

SC

RI
PT

223

Nanosized particle of silver has emerged as a promising substance in a wide range

236

of applications, including food packaging. Stable Ag nanoparticles can be ex situ

237

synthesised via the regular borohydride reduction of Ag+ ions and then dispersed into

238

a polymerisable formulation. It is however difficult due to the limitation of controlling

239

the nanoparticle monodispersity. On the other hand, nanoparticles can be in situ

240

produced in a polymerisable medium from precursors with better dispersion ability.

241

The reduction of Ag salt such as AgNO3 produces colloidal Ag with particle

242

diameters of several nanometers. The Ag nanoparticles produced by physical

243

reduction present regular shape and better dispersion, the chemical reduction, on the

244

other hand, exhibits agglomerated particles (de Azeredo 2013). Properties of nano-Ag,

AC
C

EP

235

ACCEPTED MANUSCRIPT
245

such as a low redox potential, could increase the capacity of smaller Ag nanoparticles

246

to release Ag+ compared with the equivalent bulk material. Ag nanoparticles also

247

have a novelty, which can endure high temperatures and has low volatility (Cushen et

248

al. 2013).
Nano-Ag is the most frequently used material as laundry detergents, disinfectant

250

sprays, and kitchen utensils to inhibit the growth of microorganisms on surfaces and

251

in solutions due to its broad-spectrum inhibitory activities. It is effective against

252

Gram-positive and Gram-negative bacteria, and has a significant antimicrobial

253

performance against multidrug-resistant microorganisms (Birla et al. 2009; Li et al.

254

2011). When Ag nanoparticles are incorporated and immobilised in a polymer film,

255

the particles disperse evenly and keep their nano-size into the film. Such

256

Ag-incorporated film may show antibacterial activity for prolonging foodstuff shelf

257

life, which has already been found in several commercial food contact materials.

258

Antibacterial effect in food packaging applications can thus be performed without Ag

259

nanoparticle migration, with polymer acting as carriers of nano-Ag reservoirs

260

(Llorens et al. 2012b).

TE
D

M
AN
U

SC

RI
PT

249

The small dimension, quanta and large external area effect favour interaction with

262

microbial cells, which give nano-Ag more effective antibacterial activity than the

263

normal-sized Ag particles. It was found to be 10100 times more efficient than

264

traditional AgNO3. This translated into that, to be as effective as AgNO3, only

265

0.050.5 mg mL1 of Ag nanoparticles was needed. Lara et al. (2010) reported that

266

Ag nanoparticles were able to restrain the microorganism growth from the initial

267

contact with pathogens, and showed their antibacterial effect on bacteria. Besides,

268

direct damage to cell membranes, there are basically some common proposed

269

mechanisms of the antimicrobial activity of Ag nanoparticles. Metallic nano-Ag

270

interacts with dissolved O2 and H+, inducing its antimicrobial effect. Lok et al. (2007)

AC
C

EP

261

ACCEPTED MANUSCRIPT
confirmed that the oxidised surface of Ag atoms of the Ag nanoparticles is an

272

important part to perform antimicrobial activities. Kim et al. (2007) have suggested

273

the production of reactive oxygen species by Ag nanoparticles and Ag ions as a

274

mechanism for their toxicity. In addition, metallic Ag nanoparticles can act as

275

efficient vehicles to insert within the cell membrane due to their small size and

276

subsequently feasible release Ag ions to the interior of cells in a short time, i.e. Trojan

277

Horse mechanism (Limbach et al. 2007), inhibiting DNA replication and ATP

278

production. Thus, their antibacterial activity is affected by the availability of ionic Ag

279

for bacterial contact (Magaa et al. 2008). The toxicity of Ag nanoparticles is closely

280

related to particle size. Regardless of the mechanism, best antimicrobial performance

281

was obtained from 110 nm of non-aggregated, well dispersed nanoparticles with

282

larger surface areas for Ag+ release, which have higher efficiencies of protein binding,

283

and penetrate pores in microbial membranes more easily. Moreover, aggregation

284

degree, surface charge, solubility and surface coating of Ag nanoparticle also affect

285

the antibacterial activities (Duncan 2011).

TE
D

M
AN
U

SC

RI
PT

271

Besides the antimicrobial activity, nano-Ag could catalyse the absorption and

287

decomposition of ethylene emitted from fruit metabolism, which has been postulated

288

as an ethylene blocker. Fruit and vegetable ripening caused by the gas was therefore

289

retarded with the extension of product shelf life.

291

AC
C

290

EP

286

2.3. Zinc oxide

292

ZnO nanoparticles is commercially produced by physical vapour synthesis or

293

mechanochemical processing (Casey 2006). The production can be achieved by

294

chemical reactions using different precursors as well, and synthesis methods have also

295

been used, such as hydrothermal synthesis, thermal decomposition and precipitation

296

(Espitia et al. 2012). Engineered nanoparticles of ZnO is hoped to enable its use as a
10

ACCEPTED MANUSCRIPT
more affordable and safer food packaging solution not only because of the recent

298

discovery of its biocidal activity (Emamifar et al. 2010; Emamifar et al. 2011), but

299

also white appearance, UV blocking properties and cheapness compared with Ag

300

nanoparticles. Incorporating ZnO nanoparticles in polymer materials is beneficial to

301

improve their packaging properties such as barrier properties, mechanical strength and

302

stability (Espitia et al. 2012).

RI
PT

297

In order to express the antibacterial activities, ZnO nanoparticles must contact or

304

penetrate into microbial cells. Depending on the ZnO concentration, their antibacterial

305

activities may be bactericidal or bacteriostatic. Moreover, Premanathan et al. (2011)

306

reported that ZnO nanoparticles present a more significant effectiveness on

307

Gram-positive than Gram negative microorganism. Yamamoto (2001) demonstrated

308

that ZnO shows antimicrobial effect stimulated by visible light which increases when

309

particle size decreases. The incorporation of ZnO nanoparticles in the polymer of a

310

food packaging material allows interactions between the packaging and the food, and

311

thus has a dynamic effect on its preservation (Espitia et al. 2012).

M
AN
U

TE
D

313

2.4. Titanium dioxide

EP

312

SC

303

Nano-sized TiO2 particles are synthesised by various methods, in which sol-gel

315

processing is the most common one. TiO2 is a widely studied oxide nanoparticle for

316

its UV blocking property as it is an efficient short-wavelength light absorber with

317

high photostability. TiO2 nanoparticle-incorporated food packaging films could have

318

the extra advantage of preventing food component from the oxidation by UV

319

irradiation while retaining good transparency (Duncan 2011). TiO2 nanoparticles also

320

exhibit photocatalytic activities, which are useful as self cleaning and antimicrobial

321

agents under UVA or black-light illuminations. In food processing, the biocide effect

322

of TiO2 nanocomposites with polymer materials, such as Ethylene vinyl alcohol

AC
C

314

11

ACCEPTED MANUSCRIPT
323

(EVOH) (Cerrada et al. 2008) and chitosan (Diaz-Visurraga et al. 2010), has been

324

tested. Xing et al. (2012) reported that TiO2 shows a more pronounced antibacterial

325

effect on Gram-positive than Gram-negative microorganism. In addition, TiO2

326

nanoparticles can be used to produce oxygen scavenger films (Xiao-e et al. 2004).

328

RI
PT

327
2.5. Copper/Copper oxide

Nanoparticles of elementary Cu can be generated by thermal or sonochemical

330

reduction methods from copper hydrazine carboxilate complexes in aqueous media.

331

Nanoparticles of metallic Cu are easily oxidised due to the small redox potential of

332

Cu0/Cu2+ (Llorens et al. 2012a). Combining Cu features with the size-dependent

333

enhancement of nanostructures, finely dispersed bioactive Cu nanoparticles are

334

expected to exert an improved disinfecting effect due to their size. It provides higher

335

mobility of released Cu ions, allowing them to interact closely with bacterial

336

membranes (Conte et al. 2013). CuO is mainly produced by reduction with

337

borohydride, which can be easily oxidised to show antibacterial effect in

338

ammonia-contained media (Kotelnikova et al. 2007).

TE
D

M
AN
U

SC

329

341

2.6. Carbon nanotube

Carbon nanotubes are cylinders with nanoscale diameters which may consist of

AC
C

340

EP

339

342

one-atom thick single-wall nanotube, or a number of concentric tubes which is called

343

multi-wall nanotube. Carbon nanotubes have extraordinarily high aspect ratios and

344

their elastic modulus can be as high as 1 TPa (Lau and Hui 2002). They could not

345

only be used in food packaging to enhance the mechanical properties of polymeric

346

matrices, but exert powerful antimicrobial effects, possibly because the long and thin

347

carbon nanotubes puncture the microbial cells, causing irreversible damages (Kang et

348

al. 2007).
12

ACCEPTED MANUSCRIPT
349

3.

Techniques for nanomaterial analysis

Identification, characterisation and quantification of nanomaterials in food

351

matrices are very important for research into the risks of nanoparticles to consumers.

352

Risk of a given material cannot only be quantified without an accurate description of

353

it. The functionalities of the nanomaterials can change in different food matrices,

354

depending on compounds and thermodynamic conditions. This is usually true for

355

metal nanoparticles because they need reactive surfaces to achieve their activity, and

356

thus would interact heavily with food components (Llorens et al. 2012b). More

357

detailed analytical techniques are needed to detect migration of components of

358

packaging material into foods due to the complexity among nanomaterials.

M
AN
U

SC

RI
PT

350

When measuring nanomaterials in different matrices, the analytical techniques

360

should be sensitive enough to detect low concentrations, as small particles normally

361

represent only a small part of the total mass. They are not only necessary to generate

362

data on concentration and composition but the physical and chemical properties of the

363

engineered nanomaterials within the sample. Nevertheless, the actual determination of

364

the amount of nanomaterials present in the food as consumed is not always feasible

365

because of the lack of methods for the detection of engineered nanomaterials in food

366

matrices. In such complex matrices, no single technique can provide all the

367

information; extra fractionation procedures and combined methodologies for detection

368

are needed. For example, testing of nanoparticle migration into fatty foods is

369

particularly tedious because it is difficult to isolate and determine lipophilic

370

components present at low concentrations in the fat matrix (de Abreu et al. 2010).

371

Thus, analytical methodologies must be established and standardise to detect the

372

presence of nanomaterials in foods or food simulants.

AC
C

EP

TE
D

359

373

In this section, a selection of different approaches that have been shown to be

374

applicable to the analysis of nanomaterials is discussed. Drawing examples from the

13

ACCEPTED MANUSCRIPT
375

literature, Table 2 summarises the application of these analytical techniques to

376

different media, together with the migration studies performed (refer to Section 4).

377
378

3.1. Microscopy techniques

The ideal methodologies to detect and visualise nanoparticle for various properties,

380

such as size, shape, structure, dispersion, and coagulation state are mainly electronic

381

microscope (EM) techniques and related facilities. EM techniques, based on the use of

382

accelerated electrons as a source of illumination, have a much higher resolution. The

383

most salient tools are transmission electron microscopy (TEM), scanning electron

384

microscopy (SEM) and atomic force microscopy (AFM). Depending on the technique,

385

resolutions down to 0.11 nm can be achieved. Nonetheless, since a very small

386

proportion of samples are analysed, to get a representative data, hundreds and

387

thousands of particles have to be counted, which is exacting, tiresome, and inefficient

388

(Liu et al. 2012). Moreover, EM is usually destructive, indicating that the same

389

sample cannot be further analysed by another method for verification.

TE
D

M
AN
U

SC

RI
PT

379

In TEM, electrons are transmitted through a specimen to obtain an image, which

391

provides 2D information about nanoparticles: their shape, morphology, size

392

distribution, uniformity and aggregation degree with a resolution at 0.1 nm (high

393

resolution TEM) (Llorens et al. 2012b). The high-resolution TEM can even clearly

394

demonstrate the atom layers of crystalline samples. Nevertheless, no liquid samples

395

can be placed in the TEM chamber and proper sample pretreatment is thus necessary

396

(Mavrocordatos et al. 2007). For solutions, the dehydration could cause unwanted

397

particle aggregation and changes in surface properties. Chemical fixation and a

398

straining step are often required for biological tissues and other complicated matrices

399

to keep their original state and also enhance contrast (Liu et al. 2012).

400

AC
C

EP

390

In SEM, a focused beam of electrons interacts with atoms in the sample surface,
14

ACCEPTED MANUSCRIPT
and secondary electrons, producing back-scattering electrons and characteristic

402

signals can be detected for imaging. SEM has a lower resolution than TEM, but

403

provides samples surface topography and composition. SEM device with detectors

404

able to conduct at high vacuum, or low vacuum (~2 Torr) is useful for analysing

405

biological specimens (Llorens et al. 2012b). The sample surface needs to be

406

conducting, it thus has to be coated with a layer of conductive material, but this can

407

cause the information loss. Imaging of nanoparticles in their natural state is critical for

408

nanomaterial research, none of these pretreatments can however completely avoid

409

artifacts resulting from sample drying or preparation. These artifacts can be avoided

410

by using environmental SEM (ESEM), which allows specimens to be imaged in their

411

original state without modification or pretreatment under variable humidity, up to

412

75% (Doucet et al. 2005).

M
AN
U

SC

RI
PT

401

AFM provides 3D surface information about solid or liquid samples in tapping or

414

contact modes. An oscillating cantilever is scanning over the sample surface and

415

electrostatic forces are measured between the tip and the surface. Thus, AFM is

416

capable of revealing the shape of the nanoparticles and the roughness profiles with

417

high resolution, approximately 0.5 nm, with tip dimension as the limiting factor. The

418

main strength of an AFM is that it images structures down to 0.11 nm under wet or

419

moist conditions. Nevertheless, AFM for food related samples is limited in its ability

420

to obtain qualitative or quantitative information of the sample composition (Tiede et

421

al. 2008).

AC
C

EP

TE
D

413

422
423

3.2. Spectroscopic technique

424

Spectroscopic techniques are used for nanomaterial characterisation and analysis,

425

such as determinations of the size and agglomeration in dispersions or solution from

426

1 nm to 10 m.
15

ACCEPTED MANUSCRIPT
The qualitative determination of crystalline nanomaterials can be realised by

428

applying X-ray diffraction (XRD) techniques. XRD is used to reveal data about the

429

elemental composition or crystallographic structure of natural and engineered

430

materials based on intensity of a scattered X-ray beam on the specimen. X-rays are

431

used to produce the diffraction pattern because their wavelength is typically the

432

same order of a few angstroms as the interatomic distances in crystalline solids. This

433

technique is non-destructive and complex sample pretreatment is not needed,

434

resulting in its comprehensive application in material characterisation. XRD is a

435

commonly used technique to characterise the MMT exfoliation in polymer materials

436

for packaging usages (Koo, 2006). Small angle X-ray scattering (SAXS) is an

437

analytical method derived from XRD technique. It has been applied to analyse the

438

structure of the self-assembled nanoparticles such as nanotubes, and is useful for

439

solid and liquid materials.

M
AN
U

SC

RI
PT

427

Since the optical properties of nanomaterials are different from those of

441

macroscale metal counterparts, UV-Vis spectroscopy is possible to be used for

442

nanoparticle characterisation. Due to its low cost and easy operation, UV-Vis

443

spectroscopy is applied as a supporting method to detect the presence of nanoparticles

444

and to characterise their quality. Typically, an increase in the nanoparticle

445

concentration leads to a decreasing UV-Vis transmittance. This is because that the

446

larger surface area of nanoparticles leads to an increased UV-Vis absorption

447

efficiency. The highest wavelength of UV-Vis absorption spectrum is a function of

448

the average particle size, and the information about particle dispersion can be given

449

by its full width at half-maximum (Leopold and Lendl 2003).

AC
C

EP

TE
D

440

450
451
452

3.3. Quantitative analytical techniques

Quantitative and elemental analyses of migrated nanomaterials take place mainly
16

ACCEPTED MANUSCRIPT
with inductively coupled plasma mass (ICP-MS), atomic emission (ICP-AES) and

454

optical emission spectrometry (ICP-OES). The high selectivity, sensitivity and

455

accuracy make them the most efficient techniques determining trace metal ions.

456

Sample concentration is not a limitation, the limit of detection is normally 0.110

457

ppm. Results highly depend on the sample complexity. Because of its high selectivity

458

and sensitivity, ICP-MS is more favoured than ICP-OES and ICP-AES. When the

459

nanomaterial is introduced into the ICP, the atoms of the analyte produce a flash of

460

gaseous ions in the plasma, which are measured as a single pulse by the detector and

461

appear as a spike in the graph (Echegoyen and Nern 2013). The presence of

462

nanomaterials could clog the sample tips within the spray chamber, and also the

463

existence of food components may hinder complete sample atomization, a digestion

464

process of the sample is therefore needed before the sample is pipetted and analysed.

465

Differentiating metal in the samples whether present in nanoparticulate form or ionic

466

form are key aspects that should be investigated.

TE
D

M
AN
U

SC

RI
PT

453

In the case of ICP-MS, samples cannot only be injected directly into the ion

468

source but via a combined technique, such as hydrodynamic chromatography

469

(HDC-ICP-MS) (Tiede et al. 2010) and flow field fractionation (FFF-ICP-MS)

470

(Loeschner et al. 2013). HDC separates particles on the basis of the particles

471

diffusion coefficients, which are inversely related to their hydrodynamic diameters

472

through the Stokes-Einstein equation. Minimal sample preparation is required and

473

minimal sample perturbation occurs during the passage of the sample through the

474

HDC column (Proulx and Wilkinson 2014). In FFF an external field force or gradient

475

causes differential retention of nanoparticles according to their hydrodynamic radius.

476

Following the time- and size-resolved elution, the analyte particles are carried to one

477

or several detectors. FFF is well-suited for determining the size distribution of

478

particles suspended in the food simulant used for the migration study (Schmidt et al.

AC
C

EP

467

17

ACCEPTED MANUSCRIPT
2009). However, both HDC and FFF are unable to deal with very low nanoparticle

480

concentrations at the ng/L level. Single particle ICP-MS (SP-ICP-MS) is an emerging

481

analytical technique that operates by introducing metal-based nanoparticles into the

482

ICP-MS individually and then recording the time-resolved peak for each particle

483

within each short dwell time. The intensity of the respective peaks gives information

484

about the particle size, the number of peaks gives information about the particle

485

concentration. At the same time, dissolved metal is detected as a constant signal and

486

can therefore be distinguished from the particle signal (Telgmann et al. 2014).

487

SP-ICP-MS can in theory be used to measure particle sizes of 10 nm or lower with

488

very low concentration detection limits, normally at part per trillion levels.

M
AN
U

SC

RI
PT

479

Atomic absorption spectrometry (AAS) is an effective technique, alternating ICP,

490

to detect nanomaterials, because of its high speed, precision, sensitivity, also the

491

relative cheapness. It is used mostly for quantifying the concentration of a particular

492

metal element within samples like food and biomaterials by measuring the amount of

493

energy in the form of photons of light that are absorbed by the chemical element of

494

interest. This is done by reading the spectra produced when the sample is excited by

495

radiation. Typically, the technique makes use of flame (FAAS) or graphite furnace

496

(GFAAS) to atomise the sample. A detector measures the wavelengths of light

497

transmitted by the sample, and compares them to the wavelengths which originally

498

passed through the sample (Garca and Bez 2012). Nevertheless, AAS has limited

499

linear range, and is failed for multi-element analysis (Liu et al. 2012). Another

500

particular challenge is accurately distinguishing relatively small nanoparticles from

501

dissolved ion signals.

AC
C

EP

TE
D

489

502
503
504

4.

Migration assessment of nanocomposite packaging

Migration is the mass transfer process by which low molecular mass constituents
18

ACCEPTED MANUSCRIPT
initially present in the package are released into the contained product. Since

506

packaging materials are not chemically inert and, direct contact between the package

507

and the product packaged can lead to substance migration into the product. In food

508

packaging, this process is critical since the non-intended transfer of undesirable

509

packaging constituents may affect the food safety for the consumer (Torres et al.

510

2012). In active packaging, nanomaterials may migrate into food once present in the

511

food packaging materials. The migration of nanomaterials could eventually induce

512

organoleptic changes of foods. For example, TiO2 could cause rancidity resulting

513

from lipid oxidation in lipid foods (de Azeredo 2013). The potential risk from

514

nanotechnology has to be defined better in terms of the properties of the

515

nanomaterials and their transfer rate. Because of poor packaging performance and

516

subsequent migration of nanomaterials from the packaging, ingestion of foods

517

previously in contact with nano-packaging can be an exposure route (Cushen et al.

518

2012). For investigating the possibility of applying nanomaterials to the food

519

packaging usage and assess the safety of a package in contact with foodstuffs, it is

520

necessary to carry out migration analysis under controlled conditions, which depends

521

directly on the foodstuffs or the type of food simulant tested.

EP

TE
D

M
AN
U

SC

RI
PT

505

This section reviews critically the current state of experimental and theoretical

523

investigations of migration from food packaging containing nanomaterial. Table 2

524

provides a summary of currently available migration studies for food packaging

525

nanomaterials, including study conditions and key observations.

AC
C

522

526
527

4.1. General aspects of nanomaterial migration

528

The migration process involves two stages. The initial migration must be due to

529

those nanomaterials, which are encapsulated within the surface layers. The subsequent

530

release of nanomaterial from the interior part of the specimen has to pass through
19

ACCEPTED MANUSCRIPT
voids and other gaps between the polymer molecules, which will depend on polymer

532

properties such as density, crystallinity and degree of crosslinking and branching. In

533

some cases, the nanomaterials encapsulated well inside the film need to oxidise and

534

migrate out through the polymer matrices. These nanomaterials are predominately

535

responsible for the release at later times (Huang et al. 2011).

RI
PT

531

How fast and to what extent migration of nanomaterial into food will occur

537

depend on the chemical and physical properties of food and polymer. Various factors

538

such as original concentration, particle size, molecular weight, solubility and

539

diffusivity of the specific substance in the polymer, as well as pH value, temperature,

540

polymer structure and viscosity, mechanical stress, contact time, and food

541

composition are the main controlling parameters in migration. The solubility of

542

metallic nanoparticle in aqueous solution increases with increasing temperature and

543

decreasing pH value, which will increase migration of metal in the system (Song et al.

544

2011). Migration of nanomaterial with a higher rate could be attributed to an

545

increasing diffusivity that may be expectable in polymeric matrices with lower

546

molecular weight and thus larger free volume (Schmidt et al. 2011). Migration rate of

547

a system increases when nanoparticle size and polymer dynamic viscosity decrease

548

(Cushen et al. 2012). If the food itself has a high affinity for the polymer, then it may

549

be absorbed into the package, which causes swelling or plasticisation of the polymer

550

matrix, thereby enlarging the gaps and increasing additive migration rates. For

551

instance, food components, particularly fat, that migrate into plastics, like

552

polyethylene (PE) or polypropylene (PP), will considerably increase the mobility of

553

plastic components, thus, enhancing the migration into the contained food. Organic

554

chemical additives, such as plasticisers, stabilisers, antioxidants, etc., in the plastic

555

may also migrate into food, which would reduce the solubility of nanomaterials in the

556

food matrix and further impede their migration into food (Song et al. 2011). In

AC
C

EP

TE
D

M
AN
U

SC

536

20

ACCEPTED MANUSCRIPT
557

addition, the migration of nanomaterials is sensitive to food preservation/sterilisation

558

methods. Echegoyen and Nern (2013) reported that microwave heating would

559

accelerate the migration of silver ion due to structural modification of the plastic

560

when exposed to microwaves.

Some nanomaterials have high surface area and active surface chemistry which

562

may cause chemical reactions. It is thus problematic that the use of nanomaterials may

563

give rise to formation of unexpected reaction products during the packaging material

564

fabrication (Bradley et al. 2011), or could potentiate or slow down the migration of

565

non-nano ingredients. de Abreu et al. (2010) revealed that the incorporation of clay

566

nanoparticles in a polyamide (PA) film causes a decreasing migration rate of triclosan,

567

caprolactam and trans-,trans-1,4-diphenyl-1,3-dibutadiene up to six times. It could be

568

attributed not only to the tortuous path created by the nanoparticles but to the potential

569

adhesion phenomena.

M
AN
U

SC

RI
PT

561

Nanocomposite film can not only be used for packaging but also as

571

two-dimensional delivery systems, from which migration of nutrient supplements into

572

the food can be intended. For example, packaging is able to release functional

573

additives depending on the nutritional needs and tastes, including mineral, probiotics,

574

vitamins, phytochemicals, marine oils, prebiotics and other active matter onto the

575

food surfaces in a controlled, systematic manner (Rodriguez et al. 2013). These will

576

be regarded as food additives under legislation, and could reduce the amount of

577

chemical additive needed, compared to having to distribute the additive throughout

578

the whole food (Bradley et al. 2011). These innovative technologies generally deal

579

with functional ingredients which can be directly included in the package or coating

580

materials to generate healthier foods with upgrading nutritional value through

581

migration.

AC
C

EP

TE
D

570

582
21

ACCEPTED MANUSCRIPT
583

4.2. Experimental approaches

Migration tests are an important aspect of safety assessments. Whether or not a

585

new packaging material contains nanomaterials is subject to migration test as

586

established by Commission Regulation (EU) No 10/2011 (The Council of the

587

European Communities 2011) on plastic materials contacting with foodstuff. This

588

regulation also involves The Union List: an useful annex for reference associated with

589

migrating substances (Cushen et al. 2014b). Although the best approach is to perform

590

migration test with real food matrices, since most foodstuffs have complex

591

compositions, it is analytically difficult, tedious and time consuming to directly

592

measure the migration into a food. The typical valid route to assess the mass transport

593

process is to evaluate the specific and overall migration of targeted substances using

594

food simulants according to the specifications of each case (Busolo and Lagaron

595

2012). Food simulants are selected model systems that produce similar interactions to

596

those of the food. This implies that both the extent and kinetics of mass transport

597

should be similar (Hernndez-Munoz et al. 2002). According to the norm UNE-ENV

598

13130-1 (Spanish Association for Standardisation and Certification 2005), water is

599

considered as a food simulant for a wide range of food products, such as bread, fresh

600

fruits and vegetables, meat and fish, among others. The use of slightly acidified water

601

solutions (e.g. containing 3% acetic acid) is also used as an even more aggressive

602

food simulant for acidic aqueous foods such as cola and carbonated beverages that

603

have a pH lower than 4.6 (Farhoodi et al. 2014). Alcoholic foods and beverages can

604

be simulated by a solution of 10% ethanol or actual alcoholic strength if concentration

605

exceeds 10%. Oils probably yield mass transfer data very similar to those occurring in

606

real fatty foods, but analysis is very complicated, due to the numerous oil components

607

and their non-volatility. Instead, other pure liquids are used, which vary considerably

608

in chemical nature, ranging from non-polar n-heptane or isooctane to polar

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

584

22

ACCEPTED MANUSCRIPT
609

isopropanol. In the case of water-sensitive materials intended only to contain dry

610

foodstuffs (e.g. paper, board and bioplastic), alternative tests consider the use of some

611

solid

612

polysaccharide-based gels (Mauricio-Iglesias et al. 2010).

simulants,

such

as

Tenax

(modified

polyphenylene

oxide)

and

The extractability of a component from the package can be measured by making it

614

contact with the food or food simulant at specific conditions of time, temperature and

615

static/dynamic mode (Avella et al. 2005). Time-temperature conditions are chosen

616

according to the intended use of the final food contact material or article. Council

617

Directive 97/48/EC (The Council of the European Communities 1997) establishes

618

what contact times, and temperatures are to be used in migration tests performed

619

under standardised conditions. It also allows a greater number of possible

620

combinations of times and temperatures for various processing and storage

621

conditions.

M
AN
U

SC

RI
PT

613

Migration contact can be carried out by different approaches as described in Part 1

623

of EN 1186 (British and European Standards 2002). Total immersion is the easiest

624

way to test migration. Inner and outer surfaces of material are in contact with the

625

simulant, and migration occurs from both sides. Thin material will be nearly totally

626

extracted during migration contact. The single-sided test is the most realistic way to

627

test packaging materials which are with only one side in contact with the food and

628

especially recommended for asymmetric multilayer constructions (Langowski 2008).

629

For articles in container form, it is often most convenient to test them by filling with

630

food. Sealable films can be sealed to pouches and the contact side inside can be filled

631

with simulant. As an alternative to using a pouch, a reverse pouch may be used. In

632

this case the surface intended to come into contact with the foodstuff is the outer

633

surface and the pouch is exposed to the food simulant by total immersion.

634

AC
C

EP

TE
D

622

At the end of the test, an accurate analytical method (see Section 3) is conducted
23

ACCEPTED MANUSCRIPT
to measure the target substance amount in the food/simulant, and the migration level

636

can thus be estimated. However, since there is no standardised analytical method to

637

characterise and quantify nanoparticles in food simulants or more complicated

638

matrices, using a complimentary suite of a quantitatively analytical technique, e.g.

639

ICP, with mass concentration levels down to the ng/L, modified to the food system

640

containing nanoparticles is the best approach (see Table 2) (Cushen et al. 2014b).

641

Since specific migration only concerns a given migrant, the total interaction of

642

packages with foodstuffs is better reported by overall migration, which measures the

643

total amount of all compounds migrating into foods independently of migrant

644

composition (Avella et al. 2005).

M
AN
U

SC

RI
PT

635

645
646

4.3. Theoretical approaches

Migration is a function of the mass transport parameters and the thermodynamic

648

equilibria between the contact materials and food (Torres et al. 2012). To estimate the

649

magnitude of a migration process from a packaging film into a food it is necessary to

650

know the concentration change of migrating species with time, in either the package

651

or the food. The key point of modelling migration in food contact materials is the way

652

of obtaining two fundamental parameters from the migration kinetics: the diffusion

653

and partition coefficients that are specific for each combination of migrant, package

654

and food. In most cases, migration of a substance from an elatomeric polymeric

655

packaging film above the glass transition temperature is often controlled by the

656

molecular diffusion of the migrant in the film, which can be described by Ficks

657

second law

AC
C

EP

TE
D

647

C p
t

658

=D

2C p
x 2

(1)

where Cp refers to the concentration of the migrant in the packaging material at time t

24

ACCEPTED MANUSCRIPT
and position x, and D is the diffusion coefficient which measures the rate at which the

660

diffusion process occurs, and may be either constant or concentration dependent.

661

Migration kinetics is given by the rate at which the transferred substances move

662

through the system, which can be characterised by the diffusion coefficient. The

663

uni-directional migrant transport from package to food takes place at the contact side

664

and the mass balance is described as:

V f C f
A t

= D

C p
x

(2)

SC

K pf

RI
PT

659

where Vf is the volume of food and A is the contact area. Kpf is the partition coefficient,

666

defined as the ratio of the concentration of the migrant in the packaging film and its

667

concentration in the food system (Cf) at equilibrium. The extent of the migration is

668

given by the thermodynamic equilibrium and can be measured by partition coefficient

669

(Hernndez-Munoz et al. 2002), which depends on the solubility coefficient,

670

indicating the polymer-food compatibility. For food safety, a large K limits migration

671

from packaging material to food; conversely, a lower K indicates that more migrant is

672

adsorbed into the food. To simply describe the migration process, the following

673

assumptions are often considered in the literature (Roduit et al. 2005; Stoffers et al.

674

2005; Torres et al. 2012): (1) the migrant is initially distributed homogeneously in the

675

packaging film; (2) the liquid food is well mixed so that there is no migrant

676

concentration gradient in the food; (3) the migration follows a Fickian diffusive

677

process in the packaging film and is not controlled by other kinetics steps; (4)

678

diffusion coefficient and partition coefficient are constant during migration and

679

depend only on temperature; and (5) equilibrium exists all the time during migration

680

at the interface of packaging film and food and is governed by the partition

681

coefficient.

682

AC
C

EP

TE
D

M
AN
U

665

A considerable amount of work has been devoted to modelling the transfer of

25

ACCEPTED MANUSCRIPT
substances used in the production or conversion of packaging materials (Roduit et al.

684

2005; Stoffers et al. 2005; Torres et al. 2012), such as monomers and particularly

685

additives like antioxidants and stabilisers. But to date, to the authors' best knowledge,

686

there has been relatively little work reported on the prediction of migration in

687

nanocomposite packaging. A theoretical modelling based on Ficks diffusion was

688

developed by Huang et al. (2015) that permits the prediction of the amount of

689

nanoclay migration from a multilayer nanocomposite packaging film to aqueous and

690

fatty food simulants. The model was solved using a finite element method and its

691

accuracy was successfully demonstrated by experimental validation. The model also

692

provided reliable estimates of the diffusion and partition coefficients in the system,

693

which showed an Arrhenius behaviour. There is a theoretical model put forward by

694

Simon et al. (2008), capable of predicting and quantifying nanoparticles migrating

695

from nanocomposite packaging to food based on physical and chemical properties of

696

both nanoparticles and packaging polymer materials. The result indicated that any

697

significant migration, even for a long-time contact with foods, may take place solely

698

in the case of very small nanoparticles with a radius in the order of 1 nm from

699

polymer matrices that have a relatively low dynamic viscosity, and that do not interact

700

with the nanoparticles, such as polyolefines (PE, PP). However, further tests on other

701

materials are required to establish a better understanding and to validate the modelled

702

migration behaviours for other nanocomposites. Therefore, the threshold size for

703

different migrating nanoparticles may be different since it is affected by nanoparticle

704

type and polymer matrix chemistry (Schmidt et al. 2011). Cushen et al. (2014a)

705

developed a migration and exposure model based on mathematically defined

706

migratability and subsequent migratables using the Williams-Landel-Ferry equation.

707

The model accurately predicted the nanosilver amounts obtained from the migration

708

tests. von Goetz et al. (2013) described the silver release over time using a power

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

683

26

ACCEPTED MANUSCRIPT
function and a Lagrangian particle tracking model that simulates Fickian diffusion

710

through the commercial plastic container. Bott et al. (2014) carried out a mathematical

711

modelling of the migration of carbon black nanoparticles from LDPE and PS into

712

different food simulants using the commercial software Migratest Lite 2001 software,

713

which is based on the analytical solution of Ficks second law. The results of

714

migration modelling based on theoretical considerations were in agreement with their

715

experimental findings.

RI
PT

709

717

5.

SC

716

Development of regulations for nanocomposite packaging

While nanotechnology has shown its potential to revolutionise the real-world

719

applications, a number of products have already emerged on the market in the past

720

few years. Data showed that, the commercial nanomaterial market consisted of >1000

721

manufacturer self-identified products as of 2011 (Fabrega et al. 2011). A review was

722

published dealing with emerging nanotechnologies that there appeared to be more

723

food contact products for packaging, storage, or cooking. They accounted for 17 food

724

and beverage products in the database (Woodrow Wilson International Center for

725

Scholars 2008). Besides, nearly 9,800 products containing nano-scale components

726

have been identified by the Environmental Working Group (2006). Despite the

727

incredible social and economic potential of nanotechnology, the global market faces

728

numerous hurdles in the regulation of these products. Currently, regulations of

729

nanotechnology for food industry applications are limited. This section reviews the

730

current worldwide regulatory framework used to assess the safety of nanotechnology,

731

specifically in regards to food contact materials.

AC
C

EP

TE
D

M
AN
U

718

732
733
734

5.1. European and US legal perspective on food nanotechnology

Most applications of food nanotechnology shall be subject to some form of

27

ACCEPTED MANUSCRIPT
permission process before being approved for use. There are main concerns about

736

nanotechnology based on fears regarding the reduced particle size. The small size of

737

many nanomaterials causes them to exhibit different chemical and physical

738

properties from their macroscale chemical counterparts, implying that findings of

739

toxicity studies on conventional form of large particles cannot be easily extrapolated

740

for determining their toxicity profiles (Munro et al. 2009). This is a particular

741

problem because the generally recognised as safe (GRAS) determinations were

742

likely to have been made in the absence of nanoscale safety evaluations. One

743

example is the use of nano-TiO2 to prevent food from contacting air and moisture.

744

The weight-based limits of the Food and Drug Administration (FDA) on TiO2 may

745

not adequately consider the potential hazard of nano-TiO2 (Sandoval 2009). The

746

limiting factor in conducting risk assessments of nanotechnologies is the lack of

747

bioavailability and toxicokinetics of nanomaterials. Although some engineered

748

nanomaterials have the potential to cause harm to human health, it is currently

749

unclear whether there is enough scientific evidence to apply the precautionary

750

principle to all applications of food nanotechnology. Sufficient new knowledge has

751

to be established on how nanomaterial based processes could affect human health

752

before gaining insight in their potential hazard and associated risks. Information on

753

the type of nanomaterials applied and their claimed added value for the product is

754

essential for establishing any regulation in this field to provide consistent and

755

comprehensive screening and protection for consumers.

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

735

756

Nowadays, there are no internationally agreed research protocols or standards. The

757

provision of data has not been required on particle size and some common

758

nanomaterials, such as nanoclays and metal oxides, may thus be authorised although

759

not precisely in nano-sized forms (Bradley et al. 2011). The USA and the EU are

760

examples of administrative authorities first to adapt to regulating nanotechnologies in

28

ACCEPTED MANUSCRIPT
the area of food. In the European food laws, there was no provision for the

762

development of specific regulations to regard nanomaterials as a separate class of

763

materials in 2009, but the European Parliament responded to the Commissions

764

communication on nanomaterial regulations, and contested the Commissions claim

765

that existing regulation was sufficient (European Commission 2007). An Institute of

766

Food Science and Technology (IFST) report has recommended that nanomaterials be

767

dealt with as new, potentially harmful materials, until their safety is proved. The

768

European Food Safety Authority (EFSA) stated that a prudent, case-by-case risk

769

assessment is required for substances deliberately engineered to particle size which

770

exhibit functional, physical and chemical properties that significantly differ from

771

those at a larger scale until more information is available about nanoscience and

772

nanotechnologies (EFSA 2009). The EFSA has also provided a guidance document on

773

the potential risk assessment of nanomaterials for food-related uses, which reports

774

requirements for the detection, identification and characterisation of nanomaterials

775

(EFSA 2011). Studies on in vitro and in vivo toxicity are required if it cannot be

776

proved that there is no nanomaterial migration after formulation, and also

777

nanomaterial transforms neither before nor during digestion (Llorens et al. 2012b).

EP

TE
D

M
AN
U

SC

RI
PT

761

In the USA, various federal agencies are in charge of nanotechnology-based

779

products. In 2006, the FDA formed the Nanotechnology Task Force, which is charged

780

with developing regulatory approaches to nanobased products that will ensure safety

781

and efficacy, while also facilitating beneficial technological innovation. It issued a

782

report recommending evaluation of agency guidance that could point out what data

783

manufacturer has to report to the FDA on nano-products (Silvestre et al. 2011).

784

However, the regulatory framework of the FDA is challenged by the complexities of

785

nanotechnologies and it is considered that research on risk assessment is not

786

advancing at a sufficient rate to handle progresses in nanotechnologies, since the use

AC
C

778

29

ACCEPTED MANUSCRIPT
of nanomaterials could change the legislative status of products. Developing a scheme

788

to integrate nanotechnology into the FDA-regulated products is a problem (Sandoval

789

2009). There is a gap existing between consumers expectations and commercial

790

developments about regulating nanotechnologies, despite most manufacturers of

791

industry, not surprisingly, believe that the FDAs existing legislation is adequate for

792

nano-based products. To address this shortcoming the nature of the US system of

793

regulatory authority compartmentalises the legislation of products. It is the FDAs

794

responsibility to ensure the safety of nano-based products and update its chemistry

795

guidance documents to consider substances in which size is technically critical (FDA

796

2011). Case-by-case assessment of products has been the standard since the FDAs

797

inception, and this will continue to be the case. Nonetheless, as there are currently no

798

labelling requirements, it could be difficult for the FDA to monitor nano-based

799

products and assess whether they have safety concerns (Sandoval 2009).

M
AN
U

SC

RI
PT

787

801

TE
D

800

5.2. Risk assessment and compliance of food nano-packaging

The components of plastic packaging materials require pre-market permission

803

with a safety assessment, according to chemistry and toxicity data submitted by the

804

manufacturer based on guidelines on data requirements (Bradley et al. 2011).

805

European legislation controls the compounds that can be used in the manufacture of

806

packages intended to hold food. The main EU regulatory framework stems from the

807

Regulation 1935/2004/EC (The Council of the European Communities 2004). This

808

regulation on the compliance of food contact materials is for any of its components

809

which could migrate into food with intolerable results, instead of dealing with specific

810

types of constituent. In Article 3, the risk of migration is stated where it requires that

811

any material or article intended to come into contact directly or indirectly with food

812

shall be sufficiently inert to avoid that their components are transferred into the food

AC
C

EP

802

30

ACCEPTED MANUSCRIPT
in unacceptable quantities that could harm human health, change organoleptic

814

properties of the food or deteriorate the food. To protect of the consumer health and to

815

prevent the foodstuff adulteration, two migration limits have been defined for plastic

816

materials. The overall migration limit (OML) of permitted compounds from plastics

817

to be into contact with foodstuffs is 60 mg (of substances)/kg (of food packaged or

818

food simulants) in any case (The Council of the European Communities 1990). In

819

addition, a specific migration limit (SML) restrains the migration level of those

820

substances with potential hazardous toxic effects into foods or food simulants.

821

Migration limits are on the basis of the tolerable daily intake (TDI) and acceptable

822

daily intake (ADI) recommended by the EFSA for the substance studied, and the

823

limits are assuming that, throughout the lifetime, a 60-kg human eats 1 kg of food

824

packaged in plastics containing the associated compound at the maximum approved

825

quantity every day. The EFSA regulation also provides the simulants and test

826

procedures under which relevant tests like overall migrations must be performed (The

827

Council of the European Communities 2007). For instance, the conventional value of

828

the ratio of the sample area to the simulant amount used in most cases is considered as

829

6 dm2/kg (de Abreu et al. 2010).

EP

TE
D

M
AN
U

SC

RI
PT

813

The new Regulation 450/2009/EC (The Council of the European Communities

831

2009) can be considered as a measure that lays down specific rules for active and

832

intelligent materials and articles to be applied, in addition to the general requirements

833

established in Regulation 1935/2004/EC, for their safe use. It applies to the use of

834

new types of food packaging materials improving food quality and safety of packaged

835

foods, and is broad enough to encompass nanomaterials. The regulation states that the

836

active component must be identified or supported by information on the approved

837

applications, also the maximum quantity of substances released from the active

838

component should be specified. The EFSA is empowered to conduct such assessments

AC
C

830

31

ACCEPTED MANUSCRIPT
839

and to offer a recommendation for the European Commission (Schmidt et al. 2011).

840

Authorised compounds placed on a positive list are permitted to be released from the

841

food contact material within specific limits to change the food composition or its

842

sensory properties.
Restrictions on plastic additives in terms of limits on their migration into

844

foodstuffs, in principle, are applicable also to nanomaterials. Current legislation does

845

not distinguish materials produced by nanotechnology from that routinely developed

846

by standard manufacturing methods. The nanomaterials used for manufacturing

847

nano-packaging materials are not assessed as new chemicals. The products of

848

nanotechnology are therefore treated by a combination of general EU food law and

849

more particular controls on specific substances. Nevertheless, due to possible

850

differences in the physicochemical or biological properties, the safe maximum

851

migration levels determined for macro-components shall not be applicable in the case

852

of their nano-equivalent material. Besides, not only the amount of elements should be

853

taken into account when nanomaterials are used, the specific migration of the particles

854

themselves must also be considered. Because of its highly developed surface, specific

855

toxicology issues could appear, and the migration of nanomaterials, which depends on

856

their structure and size, should be quantified instead of a mere determination of its

857

constituent elements. Consequently, for Regulations 450/2009/EC and 1935/2004/EC

858

to be valid for any potential risk from nanomaterials, pro-active testing of such

859

materials is required to identify the potential hazard and determine any dose-response.

860

It has to be determined whether the present testing protocols are effective also

861

regarding the potential migration of nanocomponents from materials into foods. The

862

EU legislation has been amended and now deals with the specific case of listed

863

substances that have been engineered as nanomaterials. In the case of the

864

nanomaterials intended for food contact, whether listed or not listed, the amendment

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

843

32

ACCEPTED MANUSCRIPT
865

states that they have to be re-assessed by the EU authorities regarding their potential

866

toxicity, and hence no specific or overall migration limits are defined at the moment

867

(Busolo and Lagaron 2012).

An example of pre-market permission was the use of titanium nitride (TiN)

869

nanoparticles in polyethylene terephthalate (PET) bottles (EFSA 2008). The EFSA

870

Scientific Panel on food contact materials adopted a positive safety opinion that TiN

871

nanoparticle is totally insoluble and chemically inert in all foods and food simulants.

872

It has been used at a level up to 20 mg/kg in PET bottles and has shown no sign of

873

migration out of the plastic down to the detection limit of 5 mg/kg for typical

874

hot-fill/pasteurisation or long-time storage at room temperature applications. Thus, it

875

is not a toxicological risk for food and toxicological data for this application are not

876

required.

M
AN
U

SC

RI
PT

868

In the case of deliberate nanomaterial intended to be released (e.g. smart

878

antimicrobial packaging), the nanomaterial should be treated as a food additive rather

879

than a packaging component and be controlled from another perspective. Labelling of

880

such packaging has to comply with the Food Additive Directive (The Council of the

881

European Communities 1989).

883
884

6.

Conclusion

AC
C

882

EP

TE
D

877

As the food packaging industry continues to remain competitive in an ever

885

expanding global market, it is believed that nanotechnologies show many advantages.

886

An emerging issue of food safety is how to deal with the compliance of all the

887

advanced nanomaterials recently developed for novel packaging applications. The

888

quality control of the packaged food and therefore the guarantee of human health are

889

imperative. Thus, more research is needed to assess whether there is a potential risk of

890

indirect food contamination through nanomaterials migration from food packaging. At

33

ACCEPTED MANUSCRIPT
891

present, the following issues should be addressed to fully assess the safety of

892

nanocomposite in food packaging: (i) thorough physicochemical properties of the

893

developed nanoparticles; (ii) methodology to determine and assess the migration

894

possibility and

895

methodologies for identifying, characterising and quantifying nanomaterials in

896

complicated food matrices; (iv) interrelationships between nanoparticle characteristics

897

and toxicity; (v) data on the toxicokinetic properties of nanoparticles after oral

898

consumption and toxicological dose-response relationships.

nanoparticles;

(iii)

consistent

and

appropriate

RI
PT

of

SC

process

The complete knowledge of the extent of food/packaging interactions during their

900

contact time will aid in controlling and limiting migration of nanomaterial. The

901

identification of the factors impacting on migration is expected to enable

902

manufacturers to more accurately improve quality assurance. Not only reduction to

903

zero of migration, but also reliable data on the nanomaterial effects on customer

904

safety after exposure will always have priority and must remain the most important

905

criterion for optimization of packaging material design and manufacturing.

TE
D

M
AN
U

899

The migration assessment of nanomaterials does not imply restraining their

907

applications in the food packaging, despite legislation and market uptake are hindered

908

by uncertainties in consumer safety. Addressing and framing the regulations of

909

nanomaterials usage for food packaging is underway through various regional and

910

international agencies. It is believed that if assessed and regulated correctly, these new

911

materials are undoubtedly important for improving the developments of product and

912

process, and warranting the consumers to enjoy hi-tech products safely in the food

913

industry. Rigorous migration assessment is critical to the success of developing

914

science-based regulations that are urgently needed.

AC
C

EP

906

915
916

Acknowledgements
34

ACCEPTED MANUSCRIPT
This work was funded by the Agency for Science, Technology and Research

918

(A*STAR), Singapore grant SERC 112-117-0038. Support from the National

919

University of Singapore (Suzhou) Research Institute under the grant number

920

NUSRI2011-007 and Jiangsu Province under the Scientific Research Platform scheme

921

is also acknowledged.

RI
PT

917

922

AC
C

EP

TE
D

M
AN
U

SC

923

35

ACCEPTED MANUSCRIPT
References
An, J., Zhang, M., Wang, S., & Tang, J. (2008). Physical, chemical and

926
927
928
929

microbiological changes in stored green asparagus spears as affected by

coating of silver nanoparticles-PVP. LWT - Food Science and Technology,
41(6), 1100-1107.
Akbari, Z., Ghomashchi, T., & Moghadam, S. (2007). Improvement in food

930
931
932
933

packaging industry with biobased nanocomposites. International Journal of

Food Engineering, 3(4), 1556-3758.
Avella, M., De Vlieger, J. J., Errico, M. E., Fischer, S., Vacca, P., & Volpe, M. G.
(2005). Biodegradable starch/clay nanocomposite films for food packaging

934
935
936
937
938

applications. Food Chemistry, 93(3), 467-474.

Birla, S. S., Tiwari, V. V., Gade, A. K., Ingle, A. P., Yadav, A. P., & Rai, M. K.
(2009). Fabrication of silver nanoparticles by Phoma glomerata and its
combined effect against Escherichia coli, Pseudomonas aeruginosa and
Staphylococcus aureus. Letters in Applied Microbiology, 48(2), 173-179.

939
940
941

Bott, J., Strmer, A., & Franz, R. (2014). Migration of nanoparticles from plastic
packaging materials containing carbon black into foodstuffs. Food Additives
& Contaminants: Part A, 31(10), 1769-1782.

942
943
944
945

Bradley, E. L., Castle, L., & Chaudhry, Q. (2011). Applications of nanomaterials in

food packaging with a consideration of opportunities for developing
countries. Trends in Food Science & Technology, 22(11), 604-610.
British and European Standards (2002). BS EN 1186-1:2002 Materials and articles

946
947
948
949
950
951

in contact with foodstuffs. Plastics. Guide to the selection of conditions and

test methods for overall migration.
Busolo, M. A., Fernandez, P., Ocio, M. J., & Lagaron, J. M. (2010). Novel
silver-based nanoclay as an antimicrobial in polylactic acid food packaging
coatings. Food Additives & Contaminants: Part A, 27(11), 1617-1626.
Busolo, M. A., & Lagaron, J. M. (2012). Oxygen scavenging polyolefin

952
953
954

nanocomposite films containing an iron modified kaolinite of interest in

active food packaging applications. Innovative Food Science & Emerging
Technologies, 16(0), 211-217.

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

924
925

955
956
957
958

Casey, P. (2006). Nanoparticle technologies and applications. In R. H. J. Hannink &

A. J. Hill (Eds.), Nanostructure control of materials (pp. 1-27). Cambridge,
UK: Woodhead Publishing Limited.
Chakraborti, M., Jackson, J. K., Plackett, D., Gilchrist, S. E., & Burt, H. M. (2012).

959
960
961

The
application
of
layered
double
hydroxide
clay
(LDH)-poly(lactide-co-glycolic acid) (PLGA) film composites for the
controlled release of antibiotics. Journal of Materials Science: Materials in
36

ACCEPTED MANUSCRIPT
Cerrada, M. L., Serrano, C., Sanchez-Chaves, M., Fernandez-Garcia, M.,

964
965
966
967

Fernandez-Martin, F., de Andres, A., Riobo, R. J. J., Kubacka, A., Ferrer,

M., & Fernndez-Garca, M. (2008). Self-sterilized EVOH-TiO2
nanocomposites: interface effects on biocidal properties. Advanced
Functional Materials, 18, 1949-1960.

968
969
970
971

Chaudhry, Q., Scotter, M., Blackburn, J., Ross, B., Boxall, A., Castle, L., Aitken, R.,
& Watkins, R. (2008). Applications and implications of nanotechnologies for
the food sector. Food Additives & Contaminants: Part A, 25(3), 241-258.
Conte, A., Longano, D., Costa, C., Ditaranto, N., Ancona, A., Cioffi, N., Scrocco, C.,

972
973
974
975

Sabbatini, L., Cont, F., & Del Nobile, M. A. (2013). A novel preservation
technique applied to fiordilatte cheese. Innovative Food Science & Emerging
Technologies, 19(0), 158-165.
Cushen, M., Kerry, J., Morris, M., Cruz-Romero, M., & Cummins, E. (2012).

976
977
978
979
980

Nanotechnologies in the food industry Recent developments, risks and

regulation. Trends in Food Science & Technology, 24(1), 30-46.
Cushen, M., Kerry, J., Morris, M., Cruz-Romero, M., & Cummins, E. (2013).
Migration and exposure assessment of silver from a PVC nanocomposite.
Food Chemistry, 139(1-4), 389-397.

981
982
983
984

Cushen, M., Kerry, J., Morris, M., Cruz-Romero, M., & Cummins, E. (2014a).
Evaluation and simulation of silver and copper nanoparticle migration from
polyethylene nanocomposites to food and an associated exposure assessment.
Journal of Agricultural and Food Chemistry, 62, 1403-1411.

985
986

Cushen, M., Kerry, J., Morris, M., Cruz-Romero, M., & Cummins, E. (2014b).
Silver migration from nanosilver and a commercially available zeolite filler

987
988

polyethylene composites to food simulants. Food Additives & Contaminants:

Part A, 31(6), 1132-1140.

989
990
991
992
993

Diaz-Visurraga, J., Melendrez, M. F., Garcia, A., Paulraj, M., & Cardenas, G.
(2010). Semitransparent chitosan-TiO2 nanotubes composite film for food
package applications. Journal of Applied Polymer Science, 116, 3503-3515.
de Abreu, D. A. P., Cruz, J. M., Angulo, I., & Losada, P. P. (2010). Mass transport
studies of different additives in polyamide and exfoliated nanocomposite

994
995
996

polyamide films for food industry. Packaging Technology and Science, 23(2),
59-68.
de Azeredo, H. M. C. (2013). Antimicrobial nanostructures in food packaging.

997
998
999

Medicine, 23(7), 1705-1713.

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

962
963

Trends in Food Science & Technology, 30(1), 56-69.

Doucet, F. J., Lead, J. R., Maguire, L., Achterberg, E. P., & Millward, G. E. (2005).
Visualisation of natural aquatic colloids and particles a comparison of
37

ACCEPTED MANUSCRIPT
conventional high vacuum and environmental scanning electron microscopy.
Journal of Environmental Monitoring, 7(2), 115-121.

1002
1003
1004
1005

Duncan, T. V. (2011). Applications of nanotechnology in food packaging and food

safety: Barrier materials, antimicrobials and sensors. Journal of Colloid and
Interface Science, 363(1), 1-24.
Echegoyen, Y., & Nern, C. (2013). Nanoparticle release from nano-silver

1006
1007
1008
1009

antimicrobial food containers. Food and Chemical Toxicology, 62, 16-22.

EFSA (2008). Opinion the 21st list of substances for food contact materials. EFSA
Journal, 888-890, 1-14.
EFSA (2009). Scientific opinion of the scientific committee on a request from the

1010
1011
1012
1013

European Commission on the potential risks arising from nanoscience and

nanotechnologies on food and feed safety. EFSA Journal, 958, 1-39.
EFSA (2011). Guidance on the risk assessment of the application of nanoscience
and nanotechnologies in the food and feed chain. EFSA Journal, 9(5), 1-36.

1014
1015
1016
1017
1018

EFSA (2012). Scientific opinion on the safety evaluation of the substance, titanium
nitride, nanoparticles, for use in food contact materials. EFSA Journal, 10(3),
26412649.
Emamifar, A., Kadivar, M., Shahedi, M., & Soleimanian-Zad, S. (2010). Evaluation
of nanocomposite packaging containing Ag and ZnO on shelf life of fresh

1019
1020
1021
1022

orange juice. Innovative Food Science & Emerging Technologies, 11(4),

742-748.
Emamifar, A., Kadivar, M., Shahedi, M., & Soleimanian-Zad, S. (2011). Effect of
nanocomposite packaging containing Ag and ZnO on inactivation of

1023
1024

Lactobacillus plantarum in orange juice. Food Control, 22(34), 408-413.

Environmental Working Group (2006). A survey of ingredients in 25,000 personal

1025
1026

care products reveals widespread use of nano-scale materials, not assessed

for safety, in everyday products.

1027
1028
1029
1030
1031

Espitia, P., Soares, N. d., Coimbra, J. d., de Andrade, N., Cruz, R., & Medeiros, E.
(2012). Zinc oxide nanoparticles: Synthesis, antimicrobial activity and food
packaging applications. Food and Bioprocess Technology, 5(5), 1447-1464.
European Commission (2007). COM(2009)607 Nanosciences and nanotechnologies:
an action plan for Europe 2005-2009. Second Implementation Report

1032
1033
1034

2007-2009.
Fabrega, J., Luoma, S. N., Tyler, C. R., Galloway, T. S., & Lead, J. R. (2011). Silver
nanoparticles: Behaviour and effects in the aquatic environment.

1035
1036
1037

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1000
1001

Environment International, 37(2), 517-531.

Farhoodi, M., Mousavi, S. M., Sotudeh-Gharebagh, R., Emam-Djomeh, Z., &

Oromiehie, A. (2014). Migration of aluminum and silicon from PET/clay
38

ACCEPTED MANUSCRIPT
1038
1039

nanocomposite bottles into acidic food simulant. Packaging Technology and

Science, 27(2), 161-168.

1040
1041
1042
1043

FDA (2011). Food ingredients and packaging: Guidance for industry.

Fernndez, A., Picouet, P., & Lloret, E. (2010a). Cellulose-silver nanoparticle
hybrid materials to control spoilage-related microflora in absorbent pads
located in trays of fresh-cut melon. International Journal of Food
Microbiology, 142(12), 222-228.

Fernndez, A., Picouet, P., & Lloret, E. (2010b). Reduction of the spoilage-related
microflora in absorbent pads by silver nanotechnology during modified
atmosphere packaging of beef meat. Journal of Food Protection, 73(12),

1048
1049
1050
1051
1052

2263-2269.
Fernndez, A., Soriano, E., Lpez-Carballo, G., Picouet, P., Lloret, E., Gavara, R.,
& Hernndez-Muoz, P. (2009). Preservation of aseptic conditions in
absorbent pads by using silver nanotechnology. Food Research International,
42(8), 1105-1112.

1053
1054
1055
1056

Garca, R., & Bez, A. P. (2012). Atomic absorption spectrometry (AAS). In M. A.

Farrukh (Ed.), Atomic Absorption Spectroscopy (pp. 1-12). Rijeka, Croatia:
InTech.
Girdthep, S., Worajittiphon, P., Molloy, R., Lumyong, S., Leejarkpai, T., &

1057
1058
1059
1060

Punyodom, W. (2014). Biodegradable nanocomposite blown films based on

poly(lactic acid) containing silver-loaded kaolinite: A route to controlling
moisture barrier property and silver ion release with a prediction of extended
shelf life of dried longan. Polymer, 55(26), 6776-6788.

1061
1062

Hernndez-Munoz, P., Catal, R., & Gavara, R. (2002). Simple method for the
selection of the appropriate food simulant for the evaluation of a specific

1063
1064

food/packaging interaction. Food Additives & Contaminants, 19(sup1),

192-200.

1065
1066
1067
1068
1069

Huang, J.-Y., Chieng, Y. Y., Li, X., Zhou, W. (2015). Experimental and
mathematical assessment of migration from multilayer food packaging
containing a novel clay/polymer nanocomposite. Food and Bioprocess
Technology, 8(2), 382-393.
Huang, Y., Chen, S., Bing, X., Gao, C., Wang, T., & Yuan, B. (2011). Nanosilver

1070
1071
1072

migrated into food-simulating solutions from commercially available food

fresh containers. Packaging Technology and Science, 24(5), 291-297.
Jin, T., & Gurtler, J. B. (2011). Inactivation of Salmonella in liquid egg albumen by

1073
1074
1075

antimicrobial bottle coatings infused with allyl isothiocyanate, nisin and zinc
oxide nanoparticles. Journal of Applied Microbiology, 110(3), 704-712.
Kang, S., Pinault, M., Pfefferle, L. D., & Elimelech, M. (2007). Single-walled

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1044
1045
1046
1047

39

ACCEPTED MANUSCRIPT
carbon nanotubes exhibit strong antimicrobial activity. Langmuir, 23,
8670-8673.

1078
1079
1080
1081

Kim, J. S., Kuk, E., Yu, K. N., Kim, J. H., Park, S. J., Lee, H. J., Kim, S. H., Park, Y.
K., Park, Y. H., Hwang, C. Y., Kim, Y. K., Lee, Y. S., Jeong, D. H., & Cho,
M. H. (2007). Antimicrobial effects of silver nanoparticles. Nanomedicine:
Nanotechnology, Biology and Medicine, 3, 95-101.

1082
1083
1084
1085

Koo, J. (2006). Polymer nanocomposites: Processing, characterization, and

application. New York, USA: McGraw-Hill.
Kotelnikova, N., Vainio, U., Pirkkalainen, K., & Seriman, R. (2007). Novel
approaches
to
metallization
of cellulose by reduction
of

1086
1087
1088
1089
1090

cellulose-incorporated copper and nickel ions. Macromolecular Symposia,

254, 74-79.
Langowski, H.-C. (2008). Permeation of gases and condensable substances through
monolayer and multilayer structures. In O. G. Piringer, & A. L. Baner (Eds.),
Plastic Packaging: Interactions with Food and Pharmaceuticals (2nd ed., pp.

1091
1092
1093
1094

297-347). Weinheim, Germany: Wiley-VCH.

Lara, H. H., Ayala-Nunez, N. V., Turrent, L. D. I., & Padilla, C. R. (2010).
Bactericidal effect of silver nanoparticles against multidrug-resistant bacteria,
World Journal of Microbiology and Biotechnology, 26, 615621.

1095
1096
1097
1098

Lau, K. T., & Hui, D. (2002). The revolutionary creation of new advanced
Materials carbon nanotube composites. Composites Part B, 33(4), 263-277.
Leopold, N., & Lendl, B. (2003). A new method for fast preparation of highly
surface-enhanced Raman scattering (SERS) active silver colloids at room

1099
1100

temperature by reduction of silver nitrate with hydroxylamine hydrochloride.

Journal of Physical Chemistry B, 107(24), 5723-5727.

1101
1102

Li, H., Li, F., Wang, L., Sheng, J., Xin, Z., Zhao, L., Xiao, H., Zheng, Y., & Hu, Q.
(2009). Effect of nano-packing on preservation quality of Chinese jujube

1103
1104
1105
1106
1107

(Ziziphus jujuba Mill. var. inermis (Bunge) Rehd). Food Chemistry, 114(2),
547-552.
Li, W. R., Xie, X. B., Shi, Q. S., Duan, S. S., Ouyang, Y. S., & Chen, Y. B. (2011).
Antibacterial effect of silver nanoparticles on Staphylococcus aureus.
Biometals, 24(1), 135-141.

1108
1109
1110

Li, X. H., Li, W. L., Xing, Y. G., Jiang, Y. H., Ding, Y. L., & Zhang, P. P. (2010).
Effects of nano-ZnO power-coated PVC film on the physiological properties
and microbiological changes of fresh-cut "Fuji" apple. Advanced Materials

1111
1112
1113

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1076
1077

Research, 152-153, 450-453.

Limbach, L. K., Wick, P., Manser, P., Grass, R. N., Bruinink, A., & Stark, W. J.
(2007). Exposure of engineered nanoparticles to human lung epithelial cells:
40

ACCEPTED MANUSCRIPT
influence of chemical composition and catalytic activity on oxidative stress.
Environmental Science & Technology, 41(11), 4158-4163.

1116
1117
1118
1119

Lin, Q.-B., Li, H., Zhong, H.-N., Zhao, Q., Xiao, D.-H., & Wang, Z.-W. (2014).
Migration of Ti from nano-TiO2-polyethylene composite packaging into food
simulants. Food Additives & Contaminants: Part A, 31(7), 1284-1290.
Liu, J.-f., Yu, S.-j., Yin, Y.-g., & Chao, J.-b. (2012). Methods for separation,

1120
1121
1122
1123

identification, characterization and quantification of silver nanoparticles.

TrAC Trends in Analytical Chemistry, 33, 95-106.
Llorens, A., Lloret, E., Picouet, P., & Fernandez, A. (2012a). Study of the antifungal
potential of novel cellulose/copper composites as absorbent materials for

1124
1125
1126
1127

fruit juices. International Journal of Food Microbiology, 158(2), 113-119.

Llorens, A., Lloret, E., Picouet, P. A., Trbojevich, R., & Fernandez, A. (2012b).
Metallic-based micro and nanocomposites in food contact materials and
active food packaging. Trends in Food Science & Technology, 24(1), 19-29.

1128
1129
1130
1131
1132

Lloret, E., Picouet, P., & Fernndez, A. (2012). Matrix effects on the antimicrobial
capacity of silver based nanocomposite absorbing materials. LWT - Food
Science and Technology, 49(2), 333-338.
Loeschner, K., Navratilova, J., Kbler, C., Mlhave, K., Wagner, S., von der
Kammer, F., & Larsen, E. H. (2013). Detection and characterization of silver

1133
1134
1135
1136

nanoparticles in chicken meat by asymmetric flow field flow fractionation

with detection by conventional or single particle ICP-MS. Analytical and
Bioanalytical Chemistry, 405, 8185-8195.
Lok, C., Ho, C. M., Chen, R., He, Q. Y., Yu, W. Y., Sun, H., Tam, P. K., Chiu, J. F.,

1137
1138

& Che, C. M. (2007). Silver nanoparticles: partial oxidation and antibacterial

activities. Journal of Biological Inorganic Chemistry, 12, 527-534.

1139
1140

Magaa, S. M., Quintana, P., Aguilar, D. H., Toledo, J. A., Angeles-Chavez, C.,
Corts, M. A., Len, L., Freile-Pelegrn, Y., Lpez, T., & Snchez, R. M.

1141
1142
1143
1144
1145

(2008). Antibacterial activity of montmorillonites modified with silver.

Journal of Molecular Catalysis A: Chemical, 281, 192-199.
Magnuson, B. A., Jonaitis, T. S. & Card, J. W. (2011). A brief review of the
occurrence, use, and safety of food-related nanomaterials. Journal of Food
Science, 76(6), 126-133.

1146
1147
1148

Mauricio-Iglesias, M., Peyron, S., Guillard, V., & Gontard, N. (2010). Wheat gluten
nanocomposite films as food-contact materials: Migration tests and impact of
a novel food stabilization technology (high pressure). Journal of Applied

1149
1150
1151

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1114
1115

Polymer Science, 116(5), 2526-2535.

Mavrocordatos, D., Perret, D., Leppard, G. G. (2007). Strategies and advances in the
characterization of environmental colloids by electron microscopy. In K. J.
41

ACCEPTED MANUSCRIPT
1152
1153

Wilkinson & J. R. Lead (Eds.), Environmental Colloids and Particles:

Behaviour, Structure and Characterization (pp. 345-404). Chichester, UK:

1154
1155
1156
1157

Wiley.
Munro, I. C., Haighton, L. A., Lynch, B. S., & Tafazoli, S. (2009). Technological
challenges of addressing new and more complex migrating products from
novel food packaging materials. Food Additives & Contaminants: Part A,
26(12), 1534-1546.

RI
PT

1158
1159
1160
1161

Nobile, M. A. d., Cannarsi, M., Altieri, C., Sinigaglia, M., Favia, P., Iacoviello, G.,
& D'Agostino, R. (2004). Effect of Ag-containing nano-composite active
packaging system on survival of alicyclobacillus acidoterrestris. Journal of
Food Science, 69(8), E379-E383.

Panea, B., Ripoll, G., Gonzlez, J., Fernndez-Cuello, ., & Albert, P. (2014).
Effect of nanocomposite packaging containing different proportions of ZnO
and Ag on chicken breast meat quality. Journal of Food Engineering, 123(0),

1166
1167
1168
1169
1170

104-112.
Premanathan, M., Karthikeyan, K., Jeyasubramanian, K., & Manivannan, G. (2011).
Selective toxicity of ZnO nanoparticles toward Gram-positive bacteria and
cancer cells by apoptosis through lipid peroxidation. Nanomedicine, 7(2),
184-192.

1171
1172
1173
1174

Proulx, K., & Wilkinson, K. J. (2014). Separation, detection and characterization of

engineered nanoparticles in natural waters using hydrodynamic
chromatography and multi-method detection (light scattering, analytical
ultracentrifugation and single particle ICP-MS). Environmental Chemistry,

1175
1176

Rodriguez, F., Sepulveda, H. M., Bruna, J., Guarda, A., & Galotto, M. J. (2013).

1177
1178

Development of cellulose eco-nanocomposites with antimicrobial properties

oriented for food packaging. Packaging Technology and Science, 26(3),

1179
1180
1181
1182
1183

149-160.
Roduit, B., Borgeat, C. H., Cavin, S., Fragniere, C., & Dudler, V. (2005).
Application of Finite Element Analysis (FEA) for the simulation of release
of additives from multilayer polymeric packaging structures. Food Additives
& Contaminants, 22(10), 945-955.

1184
1185
1186

Sandoval, B. (2009). Perspectives on FDA's regulation of nanotechnology:

Emerging challenges and potential solutions. Comprehensive Reviews in
Food Science and Food Safety, 8(4), 375-393.

1187
1188
1189

Schmidt, B., Katiyar, V., Plackett, D., Larsen, E. H., Gerds, N., Koch, C. B., &
Petersen, J. H. (2011). Migration of nanosized layered double hydroxide
platelets from polylactide nanocomposite films. Food Additives &

AC
C

EP

11, 392-401.

TE
D

M
AN
U

SC

1162
1163
1164
1165

42

ACCEPTED MANUSCRIPT
Contaminants: Part A, 28(7), 956-966.

Schmidt, B., Petersen, J. H., Bender Koch, C., Plackett, D., Johansen, N. R., Katiyar,

1192
1193
1194
1195

V., & Larsen, E. H. (2009). Combining asymmetrical flow field-flow

fractionation with light-scattering and inductively coupled plasma mass
spectrometric detection for characterization of nanoclay used in biopolymer
nanocomposites. Food Additives & Contaminants: Part A, 26(12),

1196
1197
1198
1199

1619-1627.
Silvestre, C., Duraccio, D., & Cimmino, S. (2011). Food packaging based on
polymer nanomaterials. Progress in Polymer Science, 36(12), 1766-1782.
Simon, P., Chaudhry, Q., & Bakos, D. (2008). Migration of engineered

1200
1201
1202
1203
1204

nanoparticles from polymer packaging to food a physicochemical view.

Journal of food and nutrition research, 47(3), 105-113.
Song, H., Li, B., Lin, Q. B., Wu, H. J., & Chen, Y. (2011). Migration of silver from
nanosilverpolyethylene composite packaging into food simulants. Food
Additives & Contaminants: Part A, 28(12), 1758-1762.

1205
1206
1207
1208

Sorrentino, A., Gorrasi, G., & Vittoria, V. (2007). Potential perspectives of

bio-nanocomposites for food packaging applications. Trends in Food Science
& Technology, 18(2), 84-95.
Spanish Association for Standardisation and Certification (2005). UNE-EN 13130-1

1209
1210
1211
1212

Materials and articles in contact with foodstuffs. Plastics substances subject

to limitation. Part 1: Guide to test methods for the specific migration of
substances from plastics to foods and food simulants and the determination
of substances in plastics and the selection of conditions of exposure to food

1213
1214

simulants.
Stoffers, N. H., Dekker, M., Linssen, J. H., Strmer, A., Franz, R., & Boekel, M. A.

1215
1216

J. S. (2005). Modelling of simultaneous two-sided migration into water and

olive oil from nylon food packaging. European Food Research and

1217
1218
1219
1220
1221

Technology, 220(2), 156-162.

Telgmann, L., Metcalfe, C. D., & Hintelmann, H. (2014). Rapid size

characterization of silver nanoparticles by single particle ICP-MS and
isotope dilution. Journal of Analytical Atomic Spectrometry, 29, 1265-1272.
The Council of the European Communities (1989). On the approximation of the

1222
1223
1224

laws of the Member States relating to materials and articles intended to come
into contact with foodstuffs. Official Journal of the European Union, L40,
38-44.

1225
1226
1227

The Council of the European Communities (1990). Relating to plastics materials and
articles intended to come into contact with foodstuffs. Official Journal of the
European Union, L349, 26-47.

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1190
1191

43

ACCEPTED MANUSCRIPT
The Council of the European Communities (1997). Amending for the second time
Council Directive 82/711/EEC laying down the basic rules necessary for

1230
1231
1232
1233

testing migration of the constituents of plastic materials and articles intended

to come into contact with foodstuffs. Official Journal of the European Union,
L222, 10-15.
The Council of the European Communities (2004). On materials and articles

1234
1235
1236
1237

intended to come into contact with food and repealing Directives

80/590/EEC and 89/109/EEC. Official Journal of the European Union, L338,
4-17.
The Council of the European Communities (2007). Relating to plastic materials and

1238
1239
1240
1241

articles intended to come into contact with food and Council Directive
85/572/EEC laying down the list of simulants to be used for testing
migration of constituents of plastic materials and articles intended to come
into contact with foodstuffs. Official Journal of the European Union, L91,

1242
1243
1244
1245
1246

17-36.
The Council of the European Communities (2009). On active and intelligent
materials and articles intended to come into contact with food. Official
Journal of the European Union, L135, 3-11.
The Council of the European Communities (2011). On plastic materials and articles

1247
1248
1249
1250

intended to come into contact with food Text with EEA relevance. Official
Journal of the European Union, L12, 1-89.
Tiede, K., Boxall, A. B. A., Tear, S. P., Lewis, J., David, H., & Hassellv, M. (2008).
Detection and characterization of engineered nanoparticles in food and the

1251
1252

environment. Food Additives & Contaminants: Part A, 25(7), 795-821.

Tiede, K., Boxall, A. B. A., Wang, X. M., Gore, D., Tiede, D., Baxter, M., David, H.,

1253
1254

Tear, S. P., & Lewis, J. (2010). Application of hydrodynamic

chromatography-ICP-MS to investigate the fate of silver nanoparticles in

1255
1256
1257
1258
1259

activated sludge. Journal of Analytical Atomic Spectrometry, 25(7),

1149-1154.
Torres, A., Guarda, A., Moraga, N., Romero, J., & Galotto, M. J. (2012).
Experimental and theoretical study of thermodynamics and transport
properties of multilayer polymeric food packaging. European Food Research

AC
C

EP

TE
D

M
AN
U

SC

RI
PT

1228
1229

1260
1261
1262

and Technology, 234(4), 713-722.

von Goetz, N., Fabricius, L., Glaus, R., Weitbrecht, V., Gnther, D., &
Hungerbhler, K. (2013). Migration of silver from commercial plastic food

1263
1264
1265

containers and implications for consumer exposure assessment. Food

Additives & Contaminants: Part A, 30(3), 612-620.
Woodrow Wilson International Center for Scholars (2008). Assuring the safety of
44

ACCEPTED MANUSCRIPT
nanomaterials in food packaging: the regulatory process and key issues.
Xiao-e, L., Green, A. N. M., Haque, S. A., Mills, A., & Durrant, J. R. (2004).

1268
1269
1270
1271

Light-driven oxygen scavenging by titania/polymer nanocomposite films.

Journal of Photochemistry and Photobiology A: Chemistry,162, 253-259.
Xing, Y., Li, X., Zhang, L., Xu, Q., Che, Z., Li, W., Bai, Y., & Li, K. (2012). Effect
of TiO2 nanoparticles on the antibacterial and physical properties of

1272
1273
1274
1275

polyethylene-based film. Progress in Organic Coatings, 73, 219-224.

Yamamoto O. (2001). Influence of particle size on the antibacterial activity of zinc
oxide. International Journal of Inorganic Materials, 3, 643-646.
Yang, F. M., Li, H. M., Li, F., Xin, Z. H., Zhao, L. Y., Zheng, Y. H., & Hu, Q. H.

1276
1277
1278
1279
1280

(2010). Effect of Nano-Packing on Preservation Quality of Fresh Strawberry

(Fragaria ananassa Duch. cv Fengxiang) during Storage at 4 C. Journal of
Food Science, 75(3), C236-C240.
Zhou, L., Lv, S., He, G., He, Q., & Shi, B. I. (2011). Effect of PE/AG2O
nano-packaging on the quality of apple slices. Journal of Food Quality,

SC

M
AN
U

EP

TE
D

34(3), 171-176.

AC
C

1281

RI
PT

1266
1267

45

ACCEPTED MANUSCRIPT
Manuscript submitted to Trend in Food Science & Technology
Safety assessment of nanocomposite for food packaging application
Huang, Jen-Yi a, Li, Xu b and Zhou, Weibiao a, b, c,*
a
Food Science and Technology Programme, c/o Department of Chemistry, National

University of Singapore, 3 Science Drive 3, Singapore 117543

Institute of Materials Research and Engineering, Agency for Science, Technology
and Research, 3 Research Link, Singapore 117602
National University of Singapore (Suzhou) Research Institute, 377 Linquan Street,

RI
PT

M
AN
U

SC

Suzhou Industrial Park, Jiangsu, 215123, Peoples Republic of China

*Corresponding author; e-mail: chmzwb@nus.edu.sg, tel.: +65 6516 3501, FAX: +65
6775 7895

AC
C

EP

TE
D

Tables

ACCEPTED MANUSCRIPT

Source

Nanomaterial

Carrier

Food items

Polyvinylpyrrolidone

Asparagus

RI
PT

Table 1. Representative examples of nanocomposite application in food packaging

Observation/Conclusion on developed nanocomposite

incorporated
An et al. 2008

Ag

Hindered growth of aerobic psychrotrophics, yeasts and molds, less

Emamifar et al. 2010

Ag, ZnO

Low-density polyethylene

M
AN
U

(LDPE)

Orange juice

SC

weight loss, greener colour, tenderer texture

Significantly decreased yeast and mold counts without impairing

juice relevant quality attributes

Emamifar et al. 2011

Ag, ZnO

LDPE

Orange juice

Significant reduction in Lactobacillus plantarum growth rate

Fernndez et al. 2009

Ag

Absorbent pad

Poultry meat

Confirmed antimicrobial effect against Escherichia coli and

Staphylococcus aureus

Ag

Cellulose pad

Fresh-cut melon

Lower microbial loads remained, longer microbial growth lag times

Fernndez et al. 2010b

Ag

Cellulose pad

Beef meat exudates

Reduce microbial levels

Jin and Gurtler 2011

ZnO

Allyl isothiocyanate, nisin

Liquid egg albumen

Effective inactivation in Salmonella

Li et al. 2009

Ag, TiO2, kaolin

PE

Chinese jujube

Firmer, heavier, less decay, less browning, slower ripening, decrease

in senescence and climacteric evolution

Li et al. 2010

ZnO

Polyvinyl chloride (PVC)

Fuji apple cuts

Better preservation of quality, lower counts of Escherichia coli cells

Llorens et al. 2012a

Cu

Cellulose absorber

Melon and pineapple

Excellent antifungal activity, reducing spoilage-related yeasts and

juices

moulds

Lloret et al. 2012

Ag

Absorber

Kiwi and melon juices

Reduced counts of total viable microorganisms, yeasts and molds

Nobile et al. 2004

Ag

AC
C

EP

TE
D

Fernndez et al. 2010a

PE

Apple juice

High bactericide capacity against Alicyclobacillus acidoterrestris

Yang et al. 2010

Ag, TiO2, kaolin

LDPE

Strawberry

Decelerated decay rate

Zhou et al. 2011

Ag2O

LDPE

Apple slice

Decreased microbial spoilage, delayed browning and weight loss

ACCEPTED MANUSCRIPT

Table 2. Summary of studies pertaining to migration from food nanocomposite packaging

Nano-

Main

migrant

packaging

Food/Simulant

Storage

Storage

temperature

time

Clay

Starch

Lettuce, spinach,

40 C

10 d

Carbon

LDPE, PS

3% HAc, 95% EtOH

M
AN
U

Bott et al. 2014

40, 60 C

black
Fe, clay

Lagaron, 2012

Busolo et al. 2010

HDPE,

Water, isooctane

20, 40 C

LLDPE

Ag

PLA

110 d

2, 10 d

TE
D

Busolo and

GFAAS

SC

water

3% HAc

Room

Cushen et al. 2014a

Ag

Ag, Cu

PVC

PE

EP

PLA

Saline solution

AC
C

Cushen et al. 2013

Cu

Chicken meat

Chicken breasts

Not available

The contact of the films with the vegetables did

not produce a strong increase of Fe and Mg in the
vegetables, while the higher Si contents was
observed.

FFF-ICP-MS,

Carbon black did not migrate from the packaging

MALLS

material into food simulants.

ICP-MS

Iron and aluminum migration from active

composites in direct contact with food simulants
showed very small or negligible migration levels.

18 d

ASV

temperature

Conte et al. 2013

Key observation

migration analysis

component
Avella et al. 2005

Technique for

RI
PT

Source

Partial hydrolysis of PLA from the contact

surfaces, could potentially facilitate the migration
process.

424 h

AAS

The ion release process appeared to be regulated

by first-order equation during the first hours.

5, 20 C

14 d

ICP-MS

Fill, time and temperature influenced the quantity

of silver that migrates from the nanocomposite and
that the size of nanoparticle did not.

8.13, 21.8 C

1.1, 3.1 d

ICP-MS

Effects of time and temperature on the migration

were not significant.

ACCEPTED MANUSCRIPT

Cushen et al.

Ag

PE

Water, 3% HAc

40 C

10 d

TEM, ICP-AES

Echegoyen and

Ag

Nern 2013

Commercial

50% EtOH, 3% HAc

40, 70 C

RI
PT

2014b
2 h,

plastic food

10 d

containers
Ag, ZnO

LDPE

Orange juice

4 C

28 d

Clay

PET

3% HAc

25, 45 C

790 d

Farhoodi et al.

M
AN
U

2010

2014
Huang et al. 2015

MMT

PP

Water, 3% HAc, 15%

20, 40 70 C

EtOH, olive oil,

coconut oil

Huang et al. 2011

Ag

PE

Water, 4% HAc, 95%

et al. 2010

MMT

PE

3% HAc, 50% EtOH

AC
C

Mauricio-Iglesias

TiO2

25, 40, 50 C

EP

EtOH, hexane
Lin et al. 2014

TE
D

grapeseed oil,

2 h14 d

25, 70, 100 C

simulant type were significant on silver migration.

SEM-EDX,

Migration values were much higher when heating

ICP-MS

in a microwave oven than in a conventional oven.

GFAAS

Zn migrated with a higher rate than that of silver.

ICP-OES

The concentration of dissolved silicon was always

SC

Emamifar et al.

Effects of percentage fill rate in the composite and

greater than that of dissolved aluminum.

ICP-OES

3% HAc showed the highest migration levels of

MMT among aqueous food simulants. Migration
into fatty simulants was greater than those into
aqueous ones, but independent of their fatty acid
composition.

315 d

SEM, EDX, AAS

Migrated silver in the form of spherical particles

was within 300 nm in a nano-size dimension.

18 h

ICP-MS, LPSA

The amount of Ti that migrated into 3% HAc was

higher than that into 50% EtOH. Increasing
additives in the film promoted migration of
nanoparticles.

Wheat

Water, 3% HAc, 15%

40 C

10 d

gluten

EtOH, olive oil,

the simulants after the high pressure/temperature

Tenax, agar gel

treatment.

ICP

The amount of silicon migrated was higher for all

ACCEPTED MANUSCRIPT

von Goetz et al.

Ag

Ag

2013

PLA

PE

Aqueous solution

40 C

95% EtOH

40 C

3% HAc, 95% EtOH

Commercial

Water, 3% HAc, 10%

plastic food

EtOH, olive oil

Ag2O

LDPE

ICP-MS

10 d

20, 40, 70 C

TEM, ICP-MS

19 h

20 C

containers
Zhou et al. 2011

10 d

RI
PT

Song et al. 2011

LDH

LDPE

Apple

ICP-MS

SC

Schmidt et al. 2011

ZnO, Ag

1 h10 d

M
AN
U

Panea et al. 2014

5, 15 C

224 d

ZnO migration was more common than Ag

migration.
Specific migration of LDH were higher at higher
LDH loading in the films.
The amount of Ag migration was higher in 3%
HAc than that in 95% EtOH.

SEM, TEM-EDX,

The released silver was in both ionic form, and

ICP-MS

nanoparticle form.

ICP

The PE/Ag2O bag can be used for food packaging

with acceptable safety.

LDH: layered double hydroxide; HDPE: high density PE; LLDPE: linear LDPE; PLA: polylactic acid; HAc: acetic acid solution in water; EtOH: ethanol solution in water; MALLS: multi-angle laser light-scattering

AC
C

EP

TE
D

spectrometry; ASV: anodic stripping voltammetry; EDX: energy dispersive X-ray; LPSA: laser particle size analysis

ACCEPTED MANUSCRIPT
Manuscript submitted to Trend in Food Science & Technology
Safety assessment of nanocomposite for food packaging application
Huang, Jen-Yi a, Li, Xu b and Zhou, Weibiao a, b, c, *
a
Food Science and Technology Programme, c/o Department of Chemistry, National

University of Singapore, 3 Science Drive 3, Singapore 117543

Institute of Materials Research and Engineering, Agency for Science, Technology
and Research, 3 Research Link, Singapore 117602
National University of Singapore (Suzhou) Research Institute, 377 Linquan Street,

RI
PT

M
AN
U

SC

Suzhou Industrial Park, Jiangsu, 215123, Peoples Republic of China

*Corresponding author; e-mail: chmzwb@nus.edu.sg, tel.: +65 6516 3501, FAX: +65
6775 7895
Highlights
Consumers are exposed from migrated nanomaterials from food packaging
Quantification of migration must be performed when novel food packaging is
designed
The latest studies of migration from nano-packaging into food is reviewed in

AC
C

EP

moment

TE
D

detail
Appropriate protocols of migration testing is needed for safety assessment of
nano-packaging
No specific or overall migration limits of nano-packaging are defined at the