Journal of Food Engineering 238 (2018) 1–11

Contents lists available at ScienceDirect

Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Nanotechnology in the agrofood industry T

∗
Elena Villena de Francisco, Rosa M. García-Estepa
Department of Nutrition and Food Sciences, Faculty of Pharmacy, University of Granada, Campus Universitario de Cartuja, 18012, Granada, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Nanotechnology is a great innovation that is revolutionizing the agrofood industry. It is a science that works at
Nanotechnology the nanoscale and provides many benefits; however there are disadvantages and risks associated with its use. In
Nanomaterials this study, the fundamental concepts of nanotechnology are clarified, focusing on its primary applications and a
Agrofood industry health and environment risk assessment. An analysis of the international regulatory framework is carried out,
Risk assessment
with particular focus on the European Union (EU), while the importance and impact of nanotechnology on
society is also examined.

1. Introduction Union (EU) as “any intentionally produced material that has one or
more dimensions of the order of 100 nm or less or that is composed of
The nanotechnology is a multidisciplinary science, which combines discrete functional parts, either internally or at the surface, many of
chemical and material engineering, biotechnology and industrial pro- which have one or more dimensions of the order of 100 nm or less,
cessing technology. It also plays an active role in trying to solve pro- including structures, agglomerates and aggregates, which may have a
blems such as preservation and food packaging (Cartelle and Zurita, size above the order of 100 nm but retain properties that are char-
2015). As a general definition, Martín-Gago et al. (2009) described acteristic of the nanoscale” (European Parliament and Council, 2011).
nanotechnology as “the manufacture of materials, structures, devices The main characteristic that gives nanomaterials its specific prop-
and functional systems through control and assembly of matter at na- erties is their small size, which increases the surface area, achieving a
nometre scale, and the application of new concepts and properties that higher reactivity (Cameán et al., 2010; Serena, 2016). On the other
arise as a result of a scale so small”. However, there are other defini- hand, in nanostructures we find the so-called “quantum effects”, which
tions which are more widely used and accepted, such as The Royal provide them with interesting properties, such as for example that
Society and The Royal Academy of Engineering (2004), which defined electrons that move within a nanoparticle can only possess certain
it as “the design, characterisation, production and application of energies (allowed levels of energy). As the size is reduced these energy
structures, devices and systems by controlling shape and size at nano- levels change resulting in changes in their catalytic, electrical, magnetic
metre scale”. This innovative technology has had a considerable impact or optical properties when compared to conventional formulations of
on society as it affects many sectors such as communications, textiles, the same material (Ferrari, 2005; Martín-Gago et al., 2009; Díaz del
medicine, engineering, agrofood and food technology among others Castillo, 2012; Pattan and Kaul, 2014; Serena, 2016).
(Kingsley et al., 2013; Ranjan et al., 2014; Dasgupta et al., 2015). In addition, sophisticated tools (the scanning tunnelling microscope
It is important to define which range is being used in this small and the atomic force microscope) have been developed to investigate
world. The lengthscale of interest for nanoscience and nanotechnolo- and manipulate matter at the nanoscale (The Royal Society and The
gies is from 100 nm down to the atomic level (approximately 0.2 nm) Royal Academy of Engineering, 2004). By controlling the shape, size
and includes different structures such as atoms, molecules, nano- and internal order of the nanostructures, properties (electrical con-
particles, carbon nanotubes, etc. (The Royal Society and The Royal ductivity, colour, chemical reactivity, elasticity, etc.) can be modified
Academy of Engineering, 2004; Área de Higiene Industrial, 2011; (Martín-Gago et al., 2009; Serena, 2016).
Serena, 2016). Nanomaterials are materials with morphological prop-
erties smaller than a micrometer in at least one external dimension or 2. Classification and production of nanomaterials
with a nanoscale internal structure (Díaz del Castillo, 2012). But this
definition serves only as a guide; the legislated materials are “en- The classification of nanomaterials is complex; however, several
gineered nanomaterials” (Cameán et al., 2010), defined by European groups can be distinguished according to different criteria.

∗
Corresponding author.
E-mail address: rgestepa@ugr.es (R.M. García-Estepa).

https://doi.org/10.1016/j.jfoodeng.2018.05.024
Received 9 November 2017; Accepted 23 May 2018
Available online 23 May 2018
0260-8774/ © 2018 Published by Elsevier Ltd.
E. Villena de Francisco, R.M. García-Estepa Journal of Food Engineering 238 (2018) 1–11

which are either, spherical, ellipsoidal (fullerene) cylindrical or tube

(nanotube) shaped; metal/metal oxide-based (generally spherical na-
noscale particles composed entirely or partly of one or more metals);
dendrimers (repetitively branched molecules -typically symmetrical
and spherical-which provide internal cavities for other molecules) and
quantum dots (nanocrystalline semiconductors, usually metal com-
plexes, selenides, or sulfides).

2.3. Classification according to food industry (FSAI, 2008)

Nanoparticles: can be distinguished by their chemical character-

istics, capacity to carry different ingredients and react against en-
vironmental conditions, either organic or inorganic.
Nanofibers: have a diameter of approximately 5 nm and a length of
over 15 μm and are used as a thickener in food and filtering agents.
Nanoemulsions: between 50 and 500 nm per droplet, which gives
Fig. 1. Nanomaterial fabrication methods. Modified from Área de Higiene them rheological characteristics and varying stabilities. They are used
Industrial (2011). to stabilise some ingredients, increase viscosity and encapsulate com-
ponents for subsequent release.
Nanoclay: typically made from phosphosilicate and primarily used
2.1. Classification according to origin
in food packaging, as it acts as a barrier against oxygen and carbon
dioxide. With nanoclay it possible to create lighter, thinner and more
To know the origin of nanomaterials can reveal many of their
resistant plastic.
properties. They are classified as: a) natural nanomaterials, e.g. ocean
spray (O'Dowd et al., 2004) and nanosized materials from combustion
3. Applications of nanotechnology in food
processes as forest fires and volcanic ash (Oberdörster et al., 2005). b)
Incidental or involuntarily nanomaterials generated by human activity
Nanotechnology is of great use in many fields, in particular in the
such as internal combustion engines, thermal power plants and other
agrofood industry, where is it used primarily in: primary production,
sources of thermal degradation (Oberdörster et al., 2005; Tiede et al.,
food processing and packaging and food supplements (Table 1).
2008), and c) artificial or manufactured (engineered) nanomaterials
(Oberdörster et al., 2005; Tiede et al., 2008) among which are inorganic
3.1. Primary production
(used in food and food packaging), with surface features (in packaging)
and organic (to improve the nutritional value) (Cameán et al., 2010;
Concerning primary production, nanotechnology has many appli-
FAO/OMS, 2011).
cations in varied fields from nanosensors to monitor the livestock health
Engineered nanomaterials are intentionally produced using nano-
(pigs, sheep, …) (Patil et al., 2009; Chalco, 2011; Manuja et al., 2012),
technology through the following methods (Fig. 1). The “top-down”
to control soil cultivation conditions (Plasencia, 2008; Gogos et al.,
(mechanical-physical particle production processes) approach is the
2012) and to detect pesticides in crops (Pradhan et al., 2015). Nano-
manufacturing method that reduces the size of larger materials; this is
sensors for organophosphate pesticide detection offer high sensitivity,
done by using processes such as trituration or milling; traditional source
low detect limits, super selectivity, fast responses and small sizes (Liu
materials (such as metal oxides) are pulverized using high-energy ball
et al., 2008); are used to detect residues of dichlorvos and paraoxon,
mills until a nanostructure has been produced (Raab et al., 2011). A
parathion, methyl parathion and fenitrothion (Vamvakaki and
major disadvantage is that this approach requires a great amount of
Chaniotakis, 2007; Wang and Li, 2008; Parham and Rahbar, 2010;
energy and produces waste (Mendoza and Rodríguez-López, 2007). The
Kumaravel and Chandrasekaran, 2011).
“bottom-up” approach is the construction from individual components
Nanoparticles are used for prevention, diagnosis and treatment of
(atoms or molecules) by self-assembly, using physical and chemical
livestock and poultry diseases (Chalco, 2011; Cruz and Molento, 2015;
techniques (gas- and liquid-phase). It includes aerosol processes, sol-gel
Muktar et al., 2015; Hill and Li, 2017), and to eliminate toxic residue
processes, precipitation reactions and methods such as gas condensa-
from pesticides. Aluminium oxide, lanthanum particles and nanoscale
tion, chemical vapour deposition, chemical vapour condensation, and
iron powder, absorb environmental pollutants in the process of water
solvothermal- and sonochemical methods (Charitidis et al., 2014;
purification and/or soil cleaning, increasing soil remediation capacity
Rajput, 2015) The disadvantage of the wet-chemical synthesis of na-
and reducing time and costs of the treatments (Plasencia, 2008;
nomaterials is that the desired crystalline shapes often cannot be con-
Bouwmeester et al., 2009; García et al., 2010; Khin et al., 2012).
figured and that the thermal stability of the product powder is lower.
Nanofertilizers have beneficial effects over conventional ones. This
This requires thermal post-treatment with repeated reduction of the
is the case of the use of zinc oxide nanoparticles in Zn fertilizers to
particle surface. The advantage is that the liquid phase enables highly
increase their solubility (Milani et al., 2012, 2015). De la Rosa et al.
porous materials to be produced; this would normally not be possible in
(2013) found that by applying zinc oxide nanoparticles through the
gas phase reactors due to the high temperatures. The selection of “top-
foliar spray, growth and biomass of alfalfa, tomato, and cucumber can
down” or “bottom-up” process depends on the chemical composition
be increased. The absorption and utilization of nutrients has been stu-
and the desired features specified for the nanoparticles (Raab et al.,
died by using of chitosan nanoparticles suspensions containing ni-
2011).
trogen, phosphorus and potassium fertilizers (Corradini et al., 2010;
Cota-Arriola et al., 2013; Hasaneen et al., 2014; Abdel-Aziz et al.,
2.2. Classification according to the United States environmental protection 2016). To increase the effectiveness of the treatment, urea-modified
agency hydroxyapatite nanoparticles encapsulated (Kottegoda et al., 2011) or
nanoporous zeolite-based nitrogen fertilizer (Manikandan and
Recently, the United States Environmental Protection Agency (EPA, Subramanian, 2014) can be used, that due to their slow release, can
2017) classifies engineered nanomaterials according to their chemical reduce the doses of compost.
composition and physical arrangement of the material: carbon-based, Nano encapsulation is also used for pesticides, especially for

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E. Villena de Francisco, R.M. García-Estepa Journal of Food Engineering 238 (2018) 1–11

Table 1
Applications of nanotechnology and nanomaterials in agriculture, feed and food sectors. Modified from Amenta et al. (2015).
Application Functions Use Through References

Agriculture • nutrients
Increased distribution, efficiency and controlled release of pesticides, • Nanoencapsulations Gogos et al. (2012)
or other agrochemicals. • Nanoemulsions Milani et al. (2012)
• Detection of pathogens. • Nanoparticles Cota-Arriola et al. (2013)
• Identity preservation and tracing. • Porous particles Nuruzzaman et al. (2016)
Animal feed and medicine • Improved feed quality and availability of nutrients. • Nanoencapsulated nutrients Fondevila et al. (2009)
• Elimination/reduction of pathogens. • Antimicrobial nanoparticles Andi et al. (2011)
• Improved delivery of veterinary drugs. • Nanomedicine Mouhamed et al. (2015)
Swain et al. (2016)
Hill and Li (2017)
Materials in contact with • Active and intelligent food packaging. • Biodegradable nanocomposites Paseiro et al. (2011)
food • Improved mechanical and heat resistance. • Anti-microbial metal/oxides Silvestre et al. (2011)
• Antibacterial surfaces. • Nano-sensors De Azeredo (2013)
• Increased safety and shelf life of food. Pradhan et al. (2015)
• Monitoring of packaged food Fuertes et al. (2016)
Food • Processing aids to improve texture, flavour, taste, consistency. • Nano-encapsulations Chaudhry et al. (2008)
• Improved delivery of bioactive compounds, nutrients, flavours. • Nano-emulsions Hilty et al. (2011)
• Nanoparticles Joye et al. (2014)
• Nanosized mineral salts Paredes et al. (2016)
Salvia-Trujillo et al. (2016)

hydrophobic, (their insolubility in water is a limiting factor); this tool surfaces in contact with food and kitchen utensils.
provides greater stability, improving its dispersion in aqueous media, Nanofiltration is a membrane filtration process used mostly to re-
and allowing a controlled release of the active compound, which in- move solids, including bacteria and parasites (Sekhon, 2014). Nano-
creases its effectiveness in the control of pests and reduces the doses of filtration processes are capable of removing heavy metals, natural or-
treatment in crops and human exposure (Perez-de-Luque et al., 2012; ganic matter, particles and a number of other organic and inorganic
Clemente et al., 2014; Sekhon, 2014; de Oliveira et al., 2015; Grillo substances. Is one of the main technologies to treat all kinds of water
et al., 2016; Nuruzzaman et al., 2016). including ground, surface, and wastewater or used for desalination
(Savage and Diallo, 2005; Cheng et al., 2013; Shon et al., 2013). Na-
3.2. Food and feed processing nomembranes has been successfully applied in drinking water treat-
ment plants (Cyna et al., 2002; Verliefde et al., 2007) and materials
At this stage, the application of nanotechnology enhances the such as carbon nanotubes and alumina fibers in combination with
characteristics of the product; it improves stability during processing powdered activated carbon, to remove effluent organic matter from a
and storage, and increases bioavailability of nutrients (Chaudhry et al., municipal wastewater (Kazner et al., 2008). In the food industry, na-
2008; Joye et al., 2014). nofiltration has multiple applications. Fruit juices have been tradi-
tionally concentrated by multi stage vacuum evaporation, resulting in a
loss of fresh juice aroma, changes in colour and a cooked taste due to
3.2.1. Improvement and food processing the thermal effects. Nanofiltration techniques make it possible to obtain
Nanoencapsulation and nanoemulsion formulations involve the in- products very similar to fresh, reduce and simplify the clarification
corporation, absorption or dispersion of compounds. These are used as process (Sotoft et al., 2012). The alcohol removal from beers and wines
a carrier for additives, preservatives, flavourings and food supplements, has a great importance in the beverages industry due to the increasing
so that the ingredients in the food are preserved for longer periods of demand on the non-alcoholic drinks. Membrane processes can be used
time, while maintaining stability through the gastrointestinal tract for wine production with low alcohol content (García-Martin et al.,
(Chaudhry et al., 2008; FAO/OMS, 2011; Hilty et al., 2011; McClements 2010; Catarino and Mendes, 2011). Nanofiltration application on the
and Rao, 2011; Paredes et al., 2016). The incorporated bioactive beer dealcoholization has not been reported in the literature revised.
compounds may be protected against degradation, have improved sta- These technologies are also used in the dairy industry in whey con-
bility and solubility; certain water-soluble compounds (e.g. vitamin C) centration and demineralization (Cuartas-Uribe et al., 2007; Suárez
have been rendered fat dispersible through nanocarrier technology, and et al., 2009), lactic acid separation (Li et al., 2008), and lactose re-
vice versa: fat-dispersible compounds (e.g. vitamin A) have been ren- covery (Cuartas-Uribe et al., 2010). Another application is the use of
dered water dispersible (Chaudhry et al., 2008; Bouwmeester et al., nanosilica to filter and eliminate substances that produce a sour taste in
2009; FAO/OMS, 2011; Pradhan et al., 2015). In addition, compounds some vegetable extracts (Noormans, 2010; FAO/OMS, 2011).
such as lutein, β-carotene, lycopene, vitamins A, D, E, and isoflavones
are emulsified, so that they are stable to gravitational separation and
aggregation (Magnusson et al., 2011; Pradhan et al., 2015; Salvia- 3.2.2. Manufacture of feed
Trujillo et al., 2016). Droplets surface area and solubility are greater, Nanomaterials are also used in feed manufacture, e.g. nano-ad-
and this allows enzyme digestion and absorption easier (Salvia-Trujillo ditives to protect animals against mycotoxicosis (Hassan et al., 2013;
et al., 2016). With nanoemulsions you can obtain sauces, cream, yogurt, Gholami-Ahangaran and Zia-Jahromi, 2014; Mouhamed et al., 2015),
spreads, ice creams, etc., with new consistencies, textures and flavours nano liquid vitamins mixed for in poultry and livestock feed (FAO/
and greater stability. This technology also helps produce healthier OMS, 2011) and nanoparticles that act by eliminating pathogens in the
foods, because they can create creamier textures without using much fat gastrointestinal tract (Chalco, 2011). Metal nanoparticles are added to
(Noormans, 2010; FAO/OMS, 2011; Dasgupta et al., 2015). feed (livestock and poultry) for their antimicrobial properties and po-
Nanoparticles and nanotubes are used as gelling and thickening sitive effects on growth (Fondevila et al., 2009; Andi et al., 2011; Sahoo
agents, but in particular nanoparticles help to eliminate pathogens and et al., 2014; Swain et al., 2016).
chemicals through selective binding (Kumar, 2015). The union of na-
noparticles (nanosilver) with antimicrobial properties to stainless steel
has also been studied (Chen et al., 2010), which could be applied to

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3.3. Food storage and packaging materials could be used as packaging films for a variety of oxygen-
sensitive food products, e.g. control browning of fresh-cut fruits (Li
During storage, the food can be altered by physical, chemical or et al., 2011). Nano-silver could catalyse the absorption and decom-
microbiological contaminants. Quality control and food safety checks position of ethylene emitted from fruit metabolism, which has been
must be exerted throughout the entire process. Packaging mainly aims postulated as an ethylene blocker. Fruit and vegetable ripening caused
at providing physical protection in order to prevent the food from ex- by the gas was therefore retarded with the extension of product shelf
ternal shocks and vibration, microbial infestation, temperature, oxygen life (Huang et al., 2015).
and other gases spoilage causing (Pradhan et al., 2015). Therefore, this
field constitutes most of the current market of the application of na- 3.3.3. Intelligent (“smart”) packaging
notechnology, since it can achieve greater resistance with lighter ma- A smart food packaging system may be defined as a system that
terials, in addition to a longer duration of packaged foods and less risks “perceives” some property of the packaged food and uses a variety of
for the consumer (FAO/OMS, 2011; Amenta et al., 2015). The use of mechanisms to register and transmit information about the current
nanomaterials in packaging is carried out with 3 primary objectives, quality or status of the food with regard to its safety and digestibility
improving the packaging, and develop active and intelligent packaging. (Ranjan et al., 2014). The intelligent container is able to provide in-
formation about conditions of the packaged food; it indicates whether
3.3.1. Improving packaging air inlet into a vacuum packed product, gas leaks in containers with
Nanocomposites combine polymers and nanoparticles to improve protective atmosphere, shows changes in food quality (volatile amines,
packaging; these exert antimicrobial properties and act as a barrier microorganisms, etc.) or breaking the cold chain during transportation
against temperature, humidity, gases, mechanical forces, etc. (Arora and storage (Paseiro et al., 2011; FAO/OMS, 2011). This is achieved by
and Padua, 2010; Dasgupta et al., 2015). This combination makes incorporating nanosensors, these may be able to respond to environ-
packaging more resistant, flexible (Cameán et al., 2010) and repels dirt, mental changes during storage (e.g. temperature, relative humidity and
which increases the shelf life and improves the appearance of the oxygen exposure), detect certain chemical compounds (e.g. degradation
product (Huang et al., 2015). Metal or metal oxide nanoparticles and products), pathogens, and toxins in food (Bouwmeester et al., 2009;
nanoclay are generally used. Among metal nanoparticles, silver stands Silvestre et al., 2011; Fuertes et al., 2016). The commonly used nano-
out for its antimicrobial properties (FAO/OMS, 2011; De Azeredo, sensors in the food packaging industries are time-temperature in-
2013; Amenta et al., 2015) and its great stability (Pradhan et al., 2015); tegrator and gas detector (Pradhan et al., 2015). Time-temperature
titanium dioxide for its strength as a natural barrier (FAO/OMS, 2011), indicators show colour changes that respond to both temperature and
as a photocatalytic disinfecting agent (Huang et al., 2015), and to in- exposure time. They serve to monitor exposure to inadequate tem-
hibit bad smells (Cameán et al., 2010). Aluminum nanoparticles found peratures, e.g. breakdown of the cold chain, during transport and sto-
in flexible food packaging due to its barrier property against moisture rage (Paseiro et al., 2011). Zhang et al. (2013a) have developed systems
or against gases such as carbon dioxide or oxygen. They also provide for short-lived foods based on the colour change of gold nanoparticles.
protection against ultraviolet radiation (Cameán et al., 2010). Other In the detection of gases produced due to spoilage, the nanosensors are
nanoparticles such as nano zinc oxide or carbon nanotubes are used in usually sensitive at hydrogen, hydrogen sulphide, nitrogen oxides,
food packaging, however the toxicity levels are considerably high in sulphur dioxide and ammonia. Carbon nanotubes-based gas sensors
case of carbon nanotubes and hence the use is limited (Pradhan et al., show an exceptionally high performance as well as immediate response
2015). Another option is nanoclay, layers of phosphosilicate (primarily to ammonia gas (Abdellah et al., 2013) and various gases (Su et al.,
montmorillonite) with nanometric thickness. The incorporation of 2013). This confirms that traditional packaging, which simply protects
layered silicates into polymer matrices has been used to enhance food from the external environment has become much more; a con-
polymer mechanical and barrier properties. Its main use is as a lining to tainer that maintains food characteristics for a much longer period of
prevent the gases (oxygen, carbon dioxide, moisture, and volatiles) time and is capable of relaying information regarding the micro-
(García et al., 2010; FAO/OMS, 2011). This characteristic are extremely biological quality and nutritional information of the product to the
useful for food packaging applications; their use could enhance con- consumer (Moncada, 2007).
siderably the shelf life of foods such as processed meats, cheese, con-
fectionery and cereals (García et al., 2010), as well as in extrusion- 3.4. Food supplements
coating applications for fruit juices and dairy products, or co-extrusion
processes for the manufacture of bottles for beer and carbonated drinks Nanoformulations are used in food supplements (Noormans, 2010),
(Chaudhry et al., 2008). which come in either nanomicelle or nanocapsule form as they pene-
trate quickly and contain important components for the organism, such
3.3.2. Active packaging as vitamins, minerals, omega-3 fatty acids, etc. (Plasencia, 2008;
Active packaging is designed to continuously interact with its con- Noormans, 2010). The most frequently used minerals are nanocalcium,
tents, which incorporates substances such as preservatives, anti- nanomagnesium and nanoiron (FAO/OMS, 2011). Iron nanostructures
oxidants, colorants, aromas or absorbs undesirable components such as are useful for enriching certain foods and compounds with this metal,
unpleasant smells or tastes, ethylene, oxygen, humidity, etc. (Paseiro since the deficiency of this micronutrient in human health is one of the
et al., 2011). Active packaging can inhibit microbial growth and delay most common (Hilty et al., 2011). Some examples of available com-
deterioration of the product, which improves quality and security pounds delivered in nanoemulsified form are fat-soluble vitamins D
(Huang et al., 2015). The most common nanoparticles added to confer (Guttoff et al., 2015; Ozturk et al., 2015) and E (El Kinawy et al., 2012),
antimicrobial properties are silver, chitosan, zinc oxide, magnesium coenzyme Q10 (Belhaj et al., 2012), β-carotene (Qian et al., 2012; Jo
oxide and titanium dioxide (Chaudhry et al., 2008; De Azeredo, 2013). and Kwon, 2014), and omega-3 fatty acids (Lane et al., 2014).
Nanotechnology can also contribute to decrease the deterioration of
many foods either directly or indirectly oxidation with the incorpora- 4. Health and toxicity risk assessment of nanomaterials
tion of nano oxygen scavengers. Oxidative reactions result in adverse
qualities such as off-odours, off-flavours, undesirable colour changes, Nanomaterials can provide many benefits such as improved safety,
and reduced nutritional quality. Oxygen scavengers remove O2, thereby quality and increased shelf life; however, they also have an impact on
retarding oxidative reactions (Silvestre et al., 2011). Several nano- health and the environment, as there is a direct interaction between
particles, including TiO2 (Xiao-e et al., 2004) and ZnO (Li et al., 2011) food products and nanomaterials (Amenta et al., 2015; Kumar, 2015).
were used to produce oxygen scavenger films. The nanocomposite So that nanomaterials are used appropriately, it is necessary to carry

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out a risk assessment on the effects of using nanotechnology. systems (proteins, phospholipids, nucleic acids, etc.), affecting their
properties and altering their size, shape and aggregation state of the
4.1. Risk assessment nanoparticles (Sellers et al., 2015).
Excretion: This is the elimination of nanomaterials through urine,
The risk assessment is a scientific method in which the risk is cal- faeces and saliva through the kidneys, liver or any other means of ex-
culated and it allows to identify the factors that influence said risk cretion. As with in the other phases the means of excretion depends on
(FAO/OMS, 2011). The risk assessment must take into account that the size, shape and charge of the nanomaterial (Sellers et al., 2015).
biokinetic profile and the toxicity in the target tissues can vary de-
pending on which nanomaterial is being referred to (Amenta et al., 4.1.4. Characterisation of the risk
2015). In the risk assessment, there are different stages to be carried out The negative effects on a determined population are estimated,
(FAO/OMS, 2011): taking into account the three previous phases (identification, char-
acterization of the risks and the exposure assessment) and the un-
4.1.1. Identification of the danger certainties involved in a more rigorous analysis (FAO/OMS, 2011). In
The potential negative effects on health associated with the ex- Europe the risk assessment is carried out by different bodies: the Eur-
posure of the agent are identified. Due to certain characteristics of the opean Chemicals Agency (ECHA), which guarantees the safe use of
nanomaterials, the dangers can identified with greater ease; however, chemicals, in which all nanomaterials that could pose a risk to health or
they can react in a specific way that differs to their larger counterparts ecosystems are recorded, the European Medicines Agency (EMA),
(FAO/OMS, 2011). which is in charge of authorising or rejecting the commercialisation of
medicines and the European Food Safety Authority (EFSA), which deals
4.1.2. Characterisation of the danger with the risks of nanomaterials, particularly when ingested orally
This is both a quantitative and qualitative assessment of the nature (EFSA, 2016).
of the negative effects associated with the agent. Such as in the case of
nanomaterial where there is insufficient data, a risk assessment should 4.2. Toxicity
be carried out on a case-by-case basis, which is to say determine the
factors that need to be considered based on the dose-response re- The toxic effects of nanomaterials (Table 2) are owed to their small
lationship (FAO/OMS, 2011). For example, there are factors such as the size, as this modifies absorption, distribution, metabolism and excre-
small size or the insolubility of nanomaterials, which can be of a higher tion. In addition, in also influences factors such as concentration,
toxicity that proves difficult for an organism to eliminate (Cartelle and electrical charge and interfacial characteristics (Pradhan et al., 2015).
Zurita, 2015; Kumar, 2015). Nanoemulsions have two distinct parts, (coating and cavity) due to this
they will have varying toxicity depending on the composition of each of
4.1.3. Exposure assessment the parts (Pradhan et al., 2015). In pesticides, the slow release of the
In the exposure assessment, the channel for exposure and the active components through nanocapsules or nanoemulsions implies a
amount of the agent are determined (FAO/OMS, 2011). In other words greater persistence in the organism and as a result, a greater risk. The
the toxicokinetics of the material are assessed, this includes 4 phases increased concentration of dissolvent and surfactants to form nanoe-
not including deposition: absorption, distribution, metabolism and ex- mulsions influences the fate of the pesticides, in which the decrease in
cretion (Sellers et al., 2015). active compounds in pesticides can improve environmental security by
Absorption: Absorption occurs when nanomaterials enter the circu- reducing waste and expulsion (Amenta et al., 2015). However, nano-
latory system, passing through the barriers of the human organism. This particles can cause cellular damage, deterioration of proteins, lipid
can be via inhalation, oral or dermal exposure, etc. Normally nano- peroxidation, stress and oxidative damage to DNA, inflammation and
materials are absorbed through the lungs, skin and the gastrointestinal haemolysis (Pradhan et al., 2015).
tract. Absorption can vary, depending on the channel of exposure, the
size, the shape, the charge (Sellers et al., 2015), the solubility and the 4.2.1. General mechanisms of toxicity of nanoparticles
composition of the particle (EFSA, 2016). An example can be seen in The primary mechanisms of toxicity of nanoparticles are reactive
silver nanoparticles, which due to their small size pass through the oxygen species (ROS) generation, oxidative stress, mitochondrial per-
cellular barrier and form free radicals that can cause oxidative damage turbation, inflammation, and protein denaturation, generation of
in cells and tissues. In addition these can become genotoxic, cytotoxic neoantigens, altered cell cycle regulation and DNA damage. Table 3
and carcinogenic (Pradhan et al., 2015). On the other hand, small, gold indicates the most important parameters for assessing the risks of na-
nanoparticles have been found to penetrate the intestine very quickly nomaterials to human health, including the specific properties of the
(EFSA, 2016). In other studies (Zhang et al., 2013b), it has been noted nanomaterials, such as their composition, shape, structure, area, sur-
that positively charged nanoparticles are absorbed easier than their face charge and solubility (Sellers et al., 2015). Regarding the size,
neutral or negatively charged counterparts. The studies have also Kettiger et al. (2013) observed that nanoparticles of 50 nm in size could
confirmed that smaller metallic nanoparticles with superior dissolution be introduced better than other cells, both smaller and larger. In ad-
capacities, and larger dosages had a higher absorption rate; however, dition, they noted that shape was also a determining factor, as spherical
carbon nanotubes behave inversely, due to their tendency to stick to- nanoparticles were absorbed faster than longer rod-shaped nano-
gether (EFSA, 2016). Finally, nanomaterials can pierce through layers particles. Furthermore, Reidy et al. (2013) referred to how the nano-
of skin and enter the circulatory system. Studies have found that particles charge can influence toxicity, observing that negatively
spherical nanoparticles penetrate the epidermis faster than elliptical charged particles were absorbed easier than positively charged parti-
nanoparticles. In addition, positively charged particles also facilitate cles, causing a higher cytotoxicity, however this is debatable if the type
skin penetration (Sellers et al., 2015). of cell that attacks the nanoparticle is considered (Iversen et al., 2011).
Distribution: The distribution of nanomaterials in the organism de- It has also been observed that negative particles caused damage to the
pends on the affinity of the tissues. The primary influencing factors are inside of the cell, whereas the positive only caused damage at mem-
the size and the state of aggregation. Aggregated particles are more brane level.
likely to move to pleural mesothelial cells and accumulate in the lungs
and heart; in comparison, the primary particles, have a more wide- 4.2.2. General mechanisms of toxicity of nanoparticles in food packaging
spread distribution (Sellers et al., 2015). The primary mechanism of toxicity of nanoparticles in food
Metabolism: Nanoparticles can interact with diverse biological packaging is the migration of nanoparticles from packaging to the food,

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Table 2
Some of the adverse effects of nanomaterials. Modified from Kumar (2015).
Nanomaterial Tissues/Cells and Responses References

Carbon nanotubes • Plasma membrane destabilized, oxidative stress induced and caused change in ultra-structural
morphological changes (24 mg/ml).
Shvedova et al. (2003)
Cui et al. (2005)
• Inhibited cell proliferation, induced apoptosis, reduced the ability of cell adhesion, viability loss of
embryonic renal cells (200 μg/ml).
Jia et al. (2005)
Davoren et al. (2007)
• High toxicity in macrophages in alveolar tissue, detachment of cells and change in protein
expression (single and multiwalled 22.6 μg/ml - 226 μg/ml).
Bardi et al. (2013)

• Morphological changes in lamellar structures, microvilli, tonofilaments and desmosome junctions in

relation to cell membrane.
• Inflammation in neural cells.
Metal oxides nanoparticles • Change in membrane potential, induce lipid peroxidation and oxidative stress. Possible cytotoxicity. Lin et al. (2008)
• Haemolysis of human red blood cells, atrophy of embryonic hepatic tissue (nanozinc). Shirsekar et al. (2016)
• Oxidative damage to DNA and inflammation (nanotitanium dioxide). Trouiller et al. (2009)
• Increase the levels of alkaline phosphatase, aspartate amino transferase and alanine amino
transferase enzyme activities (Iron oxide NPs).
Wu et al. (2009)

Cationic nanoscale materials NPs move across the cell membrane by forming transient opening and due to hydrophobicity, induced Verma et al. (2008)
cytotoxicity.
Silica nanoparticles Cytotoxic. Caused oxidative stress, elevated lipid peroxidation, rise in ROS (reactive oxidative species) Wang et al. (2009)
and decline in cellular glutathione (GHS).
Gold and silver nanoparticles Depolarization of α-tubulin, disturbing the cellular structure, partial fragmentation of protein. Elevated Choudhury et al. (2013), Stensberg
cholesterol and cholesterol enzyme. et al. (2011)

and thus, ingested into the human organism. The speed and to what higher levels of migration in the nanosilver-coated films. However,
extent it takes place depends on the physico-chemical properties, this general characteristics of the results for both types of containers in-
depends on the nanomaterial as much as the polymer (high tempera- dicated a low concentration of silver, therefore they suggested that it
ture, low pH, high contact period, low viscosity and structure) needed to be studied further, in order to identify whether these limits
(Almengor, 2009; Huang et al., 2015). The case that has studied been kept within the acceptable range to guarantee the safety of the con-
most frequently is silver nanoparticles. Many quantifications, using sumer (Metak et al., 2015). Furthermore, it was observed that the mi-
different methods have been carried out. Generally, the results found gration of nanomaterials occurs in two stages: first, the particles found
that migration was increased by time and temperature, but the quan- in the outer layers of the nanosilver were released; subsequently the
tities were insignificant and did not exceed the maximum established particles in the interior part migrated, passing through the spaces that
limits (Bumbudsanpharoke and Ko, 2015). In a study carried out in are left between the polymer molecules. This can facilitate diffusion and
2015 by Metak et al. (2015) the capacity and the migration levels for change to the crystalline state with simultaneous oxidation of nano-
silver nanoparticles were determined. The particles were released from silver. This induces movement in the chains so the oxidized nanosilver
packaging in the form of nanosilver impregnated polymer and coated can pass through the barrier and migrate into the food contents, in
nanosilver films, using AAS (atomic absorption spectrometry) and ICP- other words, oxidation is always necessary in nanomaterials to move
MS (inductively coupled plasma-mass spectrometry). An increase was through the polymeric matrices and reach the food contents
seen in migration when pH and storage time were raised. There were (Bumbudsanpharoke and Ko, 2015; Huang et al., 2015). One type of

Table 3
Important parameters for assessing the risks of nanomaterials to human health. Modified from Sellers et al. (2015).
Properties Effects References

Chemical Identity
Chemical composition Determines many effects EFSA (2011)
Crystalline structure Influence reactivity and affects toxicity Auffan et al. (2009)
Surface characteristics: Affects its systemic absorption upon inhalation route. Fauss et al. (2011)
• Coating The surface coating may determine the biomolecules that adhere to the nanomaterial, its distribution and
• Functionalisation cellular uptake, and the toxicity.
• Capping agents Surface charge influences the systemic distribution, uptake and toxicity.
• Surface charge
Impurities Substantially contributes to toxicity. Hull et al. (2009)
Particle Characteristics
Size Influences the degree of exposure, absorption, distribution, bioavailability and toxicity. EFSA (2011)
Shape Influences the deposition and persistence in the lungs, and the ability to penetrate a cell. Verma and Stellacci (2010)
Porosity Not identified as a primary determinant in toxicity. Hassinger and Sellers (2012)
Surface area The increase in relative surface area with decreasing particle size can increase the reactivity per unit mass of Auffan et al. (2009)
the nanoparticle.
Fundamental Behaviour
Water solubility Depends on particle size, coating, stability, manufacturing process and biological environment. For Choi et al. (2011), Ma et al.
• Rate of dissolution nanomaterials that have a high rate of dissolution, this will be an important aspect of the evaluation. (2012)
• Equilibrium solubility
Hamaker constant Zeta Potential Not important, but can influence the degree of agglomeration and sorption. SCENIHR (2009)
Dispersiveness Not important, can influence the degree of exposure (oral route). Wick et al. (2007)
Dustiness Not important, can influence the degree of exposure (inhalation). Braakhuis et al. (2014)
Activity and Reactivity
Physical hazards Not important, although may be relevant to the risk of injury in occupational exposures. Worsfold et al. (2012)
Reactivity Can impact the generation of ROS, induce inflammation and cellular toxicity. Braakhuis et al. (2014)
Photoreactivity May be relevant by dermal exposure, but is not relevant to oral or inhalation exposures. SCENIHR (2009)

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nanomaterial in which migration from the packaging to the food con- pesticides with nanoforms or nanocapsules. In the EU there is no spe-
tents is rarely detected is nanoclay, which is used in containers made cific legislation for nanomaterials in food contact materials
from polythene terephthalate (PET) (Kumar, 2015). However, other (Bumbudsanpharoke and Ko, 2015), however there are some regula-
studies have found an increase in the silicon and aluminium con- tions associated, active and intelligent materials (European
centrate when the time and temperature was increased (Farhoodi et al., Commission, 2009) and plastic materials (European Commission,
2014). In agreement with various authors, the methods used to detect 2011b, 2014). EFSA provides guidance on the use of nanomaterials in
nanoparticles in foods are still in development, however, the most the food and feed chain, and report information on detection, identi-
frequently used are ICP-MS and the inductively coupled plasma-atomic fication, characterization and risk assessment of nanomaterials (EFSA,
emission spectrometry (ICP-AES) as they are fast and efficient 2011).
(Bumbudsanpharoke and Ko, 2015). In conclusion, while concern for
the population regarding possible migration of nanomaterials into the 6. Advances and changes: industry and society
food contents, the quantities are minimal. However, there is a lack of
studies conducted on real food, as the majority are food simulators 6.1. Food sustainability
prepared for analysis (Lin et al., 2014).
One of nanotechnologies many contributions to industry and so-
4.2.3. Ecotoxicity ciety, is in the relationship between food sustainability. In the year
It is also necessary to highlight the damage that nanomaterials can 2050, Planet Earth could have over 10 thousand million inhabitants
cause to the environment, on accumulation in water or the ground. It that require a lot of food in order to sustain themselves (Jiang et al.,
affects factors such as pH, ionic strength and conductivity, the presence 2015). To achieve this it is important to prevent throwing away vast
of natural organic matter, temperature and other toxicants, among quantities of food. Nanotechnology reduces waste and increases shelf
others (Sellers et al., 2015). To achieve this, EFSa proposes to calculate life, improves food security (Handford et al., 2015; Sabourin and
the relationship between the expected concentration of nanomaterials Ayande, 2015) and above all, by using intelligent packaging, can pre-
in the environment and the expected amount of nanomaterials that vent the overprotection which is created by sell by dates (Jiang et al.,
didn't have an effect. If when divided, the fraction is greater than 1, 2015).
there is a higher risk to the environment (EFSA, 2016).
6.2. Consumer acceptance of nanotechnology
5. Nanotechnology legislation and regulation
In the small world of nanotechnology, the consumer is a key ele-
Nanotechnology has made its way into the agri-food sector and al- ment in the correct development, as their opinions can guide devel-
though many of the benefits have been addressed, researchers are opment, consequently advancing this emerging technology satisfying
aware that there are numerous risks. Due to the risks and for the con- their needs as much as possible. An important element that influences
cerns and unknowns for the population, it is important that laws and nanotechnology acceptance is the consumers’ confidence in the in-
legislations exist to regulate the most important aspects. Generally, dustrial advances (Hoobs and Goddard, 2015). To assess confidence in
there isn't a specific framework in any country, but at an international nanotechnology, many studies have been carried out to identify the
level, the safe use and production of nanomaterials is being addressed. main factors to take into account regarding their confidence and final
It can be either a binding arrangement (legislation) or not (re- acceptance.
commendations). One of the most important factors is knowledge on the topic of
EU and Switzerland are the only world regions that incorporate nanomaterial, as there is an inversely proportional relationship be-
nanotechnology into current legislation, while other countries simply tween knowledge and mistrust (Handford et al., 2015). This could be
carry out recommendations with regards to the use of this technology due to a personal lack of knowledge or due to the lack of information
(Amenta et al., 2015). The main aspects, which are being addressed by provided by the food industry (Roosen et al., 2015).
EU legislation include the definition of nanomaterial, the requests for On the other hand, another important factor is the type of con-
authorization (enclosing risk assessment and management), traceability sumer. Two different types of consumer have been established and
and labelling (Amenta et al., 2015). studied: those with skeptical and those with altruistic attitudes (Brown
A definition of “nanomaterial” was recommended by the European et al., 2015). Those with skeptical attitudes perceive a greater risk to-
Commission: “Nanomaterial means a natural, incidental or manu- wards food modified through nanotechnology, due to the sensation of
factured material containing particles, in an unbound state or as an fear and confusion that skepticism can cause (Brown et al., 2015). As a
aggregate or as an agglomerate and where, for 50% or more of the result, this group must be direct participants at the time of establishing
particles in the number size distribution, one or more external dimen- a regulation for nanotechnology in the food industry (Roosen et al.,
sions is in the size range 1 nm–100 nm” (European Commission, 2015). However for consumers with altruistic attitudes, the risks of
2011a). This definition is only recommendation. Food information law nano-foods are insignificant in comparison to the benefits (Brown et al.,
(European Parliament and Council, 2011) includes the definition of 2015).
engineered nanomaterial and all ingredients present in the form of Furthermore, in the economic domain, it has been observed that
engineered nanomaterials shall be clearly indicated in the list of in- when buying products with health benefits, the consumer opted for
gredients. The names of such ingredients shall be followed by the word products with natural additives; whereas in the case of products with no
“nano” in brackets. This results in greater transparency about the use benefits, consumers would rather the product had been manipulated
and exposure of nanomaterials and better traceability, giving the con- using nanotechnology (Brown et al., 2015; Roosen et al., 2015).
sumer more confidence. However, labelling nanomaterials could po- As a result, some consumers see nanotechnology as a solution to
tentially be confused as hazard labelling (Amenta et al., 2015). In ad- some current problems; while others believe that it needs to be in-
dition, nanotechnology is included in the latest regulation relative to vestigated further to eliminate any possible risks before widespread
novel foods (European Parliament and Council, 2015); it indicates that implementation of nanotechnology in the industry (Handford et al.,
“to ensure a high level of protection of human health and consumers' 2015). In addition, more information is needed on what the population
interests, food consisting of engineered nanomaterials should also be thinks is a benefit and what a risk (Giles et al., 2015). While nano-
considered a novel food”. technology looks promising in many agro-industry areas, to achieve this
On the other hand, the risk assessment is important, requires an it needs a confidence boost through clear and transparent information
analysis and an request for the authorization each product, e.g. and regulation and risk assessment of the use of nanotechnology in this

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sector (Giles et al., 2015; Handford et al., 2015). broilers. Global Vet. 7 (6), 605–609. https://idosi.org/gv/GV7(6)11/14.pdf.
Área de Higiene Industrial, 2011. La seguridad y salud en la exposición a nanopartículas.
Instituto Riojano de Salud Laboral, Logroño. http://www.larioja.org/es/upload/
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one of the fields that is most affected by this ground-breaking tech- Bianco, A., Pizzorusso, T., Kostarelos, K., 2013. Functionalized carbón nanotubes in
nology is the agrofoods industry. The use of nanomaterials in the food the brain: cellular internalization and neuroinflammatory responses. PLoS One 8
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from the production of primary materials, up until the food is on the
2012. Formulation characterization and pharmacokinetic studies of coenzyme Q10
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Manufacturing nanomaterials: from research to industry. Manuf. Rev. 1 (11).
https://doi.org/10.1051/mfreview/2014009.
Authors declare that there are no conflicts of interest. This research Chaudhry, Q., Scotter, M., Blackburn, J., Ross, B., Boxall, A., Castle, L., Aitken, R.,
did not receive any specific grant from funding agencies in the public, Watkins, R., 2008. Applications and implications of nanotechnologies for the food
sector. Food Addit. Contam. 25 (3), 241–258. https://doi.org/10.1080/
commercial, or not-for-profit sectors.
02652030701744538.
Chen, L., Zheng, L., Lv, Y., Liu, H., Wang, G., Ren, N., Liu, D., Wang, J., Boughton, R.I.,
Acknowledgement 2010. Chemical assembly of silver nanoparticles on stainless steel for antimicrobial
applications. Surf. Coating. Technol. 204 (23), 3871–3875. https://doi.org/10.1016/
j.surfcoat.2010.05.003.
Authors wish to thank Danielle Grinstead for her professionalism in Cheng, R.C., Tseng, T.J., Wattier, K.L., 2013. Two-pass Nanofiltration Seawater
English translation. And the Elena Villena de Francisco is also grateful Desalination Prototype Testing and Evaluation. Desalination and Water Purification
to her family for the unconditional support and to Rocío and José Research and Development Report No. 158. U.S. Department of the Interior, pp. 334.
https://www.usbr.gov/research/dwpr/reportpdfs/report158.pdf.
Manuel for knowing how to listen and to be by my side at the right Choi, J., Reipa, V., Hitchins, V.M., Goering, P.L., Malinauskas, R.A., 2011.
time. Physicochemical characterization and in vitro hemolysis evaluation of silver nano-
particles. Toxicol. Sci. 123 (1), 133–143. https://doi.org/10.1093/toxsci/kfr149.
Choudhury, D., Xavier, P.L., Chaudhari, K., John, R., Dasgupta, A.K., Pradeep, T.,
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