Cold plasma technology is also known as non-thermal plasma technology. It is a relatively new technology in terms of its application in post-harvest technology and food processing sector. Treatment of food products with cold plasma technology is very much needed for food products which are not suitable to be sterilized using heat, chemicals or other conventional processing tools. Generally high nutrient food is needed to be plasma disinfected to avoid nutrient loss
(Misra et al., 2015).
There are some other methods of non-thermal processing techniques which include gamma irradiation, ozonation, beta irradiation, power ultrasound, UV treatment, pulsed light, pulsed electric field (PEF), high hydrostatic pressure
etc. Most of these techniques are commercially viable and considerably economically feasible. But there are some disadvantages associated with these processes. Some methods like treatments of gamma irradiation, UV treatment and high energy electron beams are limited in practice because of economic feasibility and very high initial investment. Purely physical techniques such as high hydrostatic pressure are chemically safe but require complex equipments
(Rastogi et al., 2007) and its ability to work in case of fresh fruits and vegetables
(Kruk et al., 2009). Not all these methods are capable to microbiologically sterilize contaminated fruit and vegetables. Other modern techniques of disinfections like power ultrasound, UV treatment, pulsed light, ozonation and electric discharge are known as Advanced Oxidation Processes
(Niemira et al., 2008). Pulsed UV light technology have wide application in microbial inactivation and surface disinfection of packaging materials, but it demonstrates limitations due to shadowing effects in food products (
Gómez-López et al., 2007). However there are several methods for sterilization of fresh and processed food products but till there is no ideal technology to achieve sterilization of multiple products at ambient temperature other than non-thermal plasma (NTP) or cold plasma
(Basaran et al., 2008; Selcuk et al., 2008). Hence this technology has recently drawn considerable attention of post-harvest technologists and food scientists.
Losses in fresh horticultural produce and processed food products are enormous till today. With increasing population, it is a tedious task to ensure safe and nutritionally stable food to all the population. Non-thermal plasma can significantly reduce loss and wastage of fresh and processed horticultural products, cereals, pulses, meat and dairy products. Gradually there is a shift of food habit and perception of food from just being a satire to stomach to a nutritionally balanced diet. With increasing arena of food technology, new risks are also found including micro-organism safety, changing production technologies and an increase of the global trade of food stuffs
(Havelaar et al., 2010).
Plasma and its properties
An American scientist ‘Irving Langmuir’ in the year 1928 proposed that electrons, neutrals and ions in an ionized gas are similar to a corpuscular material entrained in some kind of fluid medium. This entraining medium was termed as ‘plasma’. But later it was found that there is actually no specific fluid medium which are entraining the electrons, neutrals and ions in an ionized gas (
Bellan, 2006).
Plasma is more similar to gas than solid or liquid. Properties showed by plasma are quite different from solid, liquid and gas. When energy is supplied, matter changes its state from solid to liquid to gas and ultimately to plasma. When gases are heated sufficiently to higher energies thus that the intra-atomic and molecular structures get loosen, it breaks down resulting in the formation of free electrons and ions. Plasma is partially or solely ionized gas composed of free electrons, neutrals and ions. Plasma contains equal number of positive charge carrier and negative charge carrier and hence is neutral charged
(Misra et al., 2011; Kudra and Mujumdar, 2009). In other words, plasma can be defined as a hot ionized gas into which if sufficient energy is provided, the electrons can be freed from atoms/molecules. In plasma both ions and electrons usually co-exist along with a cloud of active particles. This retains the imparted energy for specific time duration and then discharges it as visible/ultraviolet (UV) light during the process of recombination. Hence plasma is often specified to as the fourth state of matter. In the universe more than 99% of visible matter is composed of plasma. Unlike gases plasma is in ionized state and hence it is a good conductor of electricity.
On the basis of relative energy levels of electrons and constituent species, plasma is either hot plasma or cold plasma. Hot plasma is also known as thermal plasma and cold plasma is known as non-thermal plasma. Hot plasma has electrons and other heavy particles at thermodynamically equilibrium stage. Hot plasmas are produced in atmospheric arcs, sparks and flames. Cold plasma or non-thermal plasma is less well ionized as compared to thermal plasma. Cold plasma is generated under atmospheric pressure (1 bar) or at vacuum when a temperature of 30-60°C is maintained. Unlike thermal plasma, non-thermal plasma is not thermodynamically equilibrium.
Production of plasma
At earlier days, the entire plasma treatment was carried out under vacuum or low pressure condition. But now atmospheric pressure plasma system has been developed. This process is very much economical, technically feasible and industrially acceptable
(Yun et al., 2010). The capability to produce plasma at atmospheric pressure has made the system much more industrially acceptable because of its lowered input cost
(Kim et al., 2011).
Plasma is known to develop when inert gas comes in contact with electricity. In this entire process the charged particles, neutrons, free radicals and several radiations are generated. The whole formulation is known as plasma. The gas that can be used to generate plasma may include a single gas or a mixture of some gases. Oxygen, nitrogen, helium, argon and neon are the gases which can be used for plasma generation. However the quality depends on the type of gas or its combination used.
In case of non-thermal plasma or cold plasma, the electron temperature is much higher than that of the positive ions and neutral particles. As there is a difference in thermal equilibrium so a NTP cannot be said to be as thermodynamic equilibrium. NTP can be generated by an electric discharge in a gas at lower pressure or using microwaves. The temperature in this case should be within 30-60°C. Some common instance of plasma generation at atmospheric pressure includes the dielectric barrier discharges (DBD), corona discharge, radio-frequency plasmas (RFP) and the gliding arc discharge. In contrary, thermal plasmas are generated at higher pressures which also require high power and an almost thermal equilibrium exists between the electrons, positive ions and neutral particles. In case of post-harvest sector and food industries, non-thermal plasma (cold plasma) is needed. This is produced at atmospheric pressure (1 bar) or lower.
Types of plasma
In the last 3 decades, there are numerous techniques that were being developed to produce non-thermal plasma. This includes radio frequency (RF), dielectric barrier discharges (DBD), corona discharges (CD), gliding arc discharges (GAD), plasma spray, plasma needle and atmospheric pressure plasma jet (
Stepczynska, 2016).
A. Radio frequency discharges (RF) plasmas
Radio-frequency discharges are obtained when gas is subjected to an oscillating electromagnetic field. The field is generated by an induction coil surrounding the reactor (inductive discharge) or by separate electrodes is arranged on the external surface of the reactor (capacitive discharge).
B. Corona discharges (CD) plasmas
Corona discharges generated through asymmetric electrode pair, where relatively high voltage occupies the region of one electrode which exceed the breakdown strength of gas and creates weakly ionized plasma in surrounding of electrode.
C. Dielectric barrier discharges (DBD)
DBD discharge can be produced in different mediums at high frequency and high electric discharge through ionization and produces non-equilibrium plasma at atmospheric pressure.
D. Gliding arc discharge plasmas
The plasma is produced by injecting the gas between two electrodes and resultant generated arc at the shorter electrode distance, blown to electrodes and broken into plasma.
E. Microplasma
Microplasma is a miniature version of plasma in which the dimensions of the plasma can range between tens, hundreds, or even thousands of micrometers in size. Recently the micrometer range plasmas has gain much attention as it enables rapid reactive species generation at atmospheric temperature and relatively low power (1 W) consumption.
F. Plasma spray and plasma needle plasmas
The plasma needle is a type of non-thermal atmospheric glow discharge; it has a single electrode configuration and is operated in helium.
Utilization of cold plasma
Non-thermal plasma technology is having multipurpose utilization potential in post-harvest technology and food technology sector. Initially the application of cold plasma technology was applicable to microbial disinfection, but now it have a wide application including the aspects discussed below:
Disinfection/Decontamination/microbial inactivation
The efficiency of plasma to serve as a de-contaminant came to notice in the year 1968 (
Menashi, 1968). It was the year 1989, when the efficacy of O
2 as an anti-bacterial agent was showcased (
Nelson and Berger, 1989;
Niemira, 2012). Later on it was found that cold plasma technology can also have lethal effect on spores
(Lee et al., 2006) and viruses as well
(Terrier et al., 2009).
Oxygen based plasma at pressure lower than atmosphere was found highly effective against pathogenic microbes as it causes lipid oxidation, protein denaturation and DNA alteration of microbial cells. The outer surface of the microbial cells contains unsaturated fatty lipid which gets oxidized as soon as it comes with contact to plasma
(Guzel-Seydim et al., 2004). The oxidative species which are produced during the plasma discharge process (reactive oxygen and nitrogen species) leads to peroxidation of lipids and oxidation of proteins and DNA
(Montie et al., 2000). Atomic oxygen is a 10
6 stronger oxidative agent as compared to oxygen molecular. The oxidative potential of oxygen and nitrogen can be understood by understanding their reactive ionic species like O
• (singlet oxygen), O
2 (atomic oxygen), O
3 (ozone), hydroxyl (OH), hydroxyl radicals (OH
•), nitric oxide (NO
•), nitrogen dioxide (NO
2), dinitrogen pentoxide (N
2O
5) and UV photons
(Ziuzina et al., 2015; Sakiyama et al., 2012). Lysis of cells can also take place due to oxidation of amino acids and nucleic acids
(Critzer et al., 2007).
Not only oxidation of lipid bi-layer but the bombardment of radicals or the charged particles have significant potential to cause lysis of microbial cells. The bombardment of the radicals causes the cells to rapture
(Laroussi et al., 2003). The cells would also get raptured due to persisting electrostatic forces on the cell membrane
(Mendis et al., 2002). UV photons that are released during plasma treatments causes dimerization of thymine base of the DNA of the fungal cells and spores
(Boudam et al., 2006; Misra et al., 2018).
In an experiment it was observed that UV-C radiation that was released during the process is one of the most effective in the inactivation of microorganisms
(Roth et al., 2010). Another feature of this technology is the capability to have plasma treatment even inside a sealed package. This approach is referred as the “in-package plasma technology” and can be an alternative to canning and high pressure processing.
A. Fresh horticulture produces
The application of cold atmospheric pressure plasma (CAPP) is an innovative non-thermal technology for inactivating undesirable microorganisms which are present on food products. As this method does not promote application of heat so it can be effectively used in case of heat-sensitive products. Denaturation of desirable components including thermo labile vitamins and amino-acids are not affected. Some instances of Disinfection of fresh horticulture produces are mentioned in Table 1.
B. Processed products
Plasma technology is also known to decontaminate processed products of horticultural crops as well. Some instances of disinfection of processed products are mentioned in Table 2.
C. Cereals and pulses
Non-thermal cold-plasma technology is also known to decontaminate cereals and pulses as well. Some instances of disinfection of processed products are mentioned in Table 3.
Sterilization of packaging materials and in-package decontamination
The purpose of packaging is not only containment but also preservation and protection during handling, storage and transportation. In the entire process, packaging material can also get contaminated with pathogens. These pathogens get transferred to the produce in mean time and can spoil the food or cause serious health hazard (
Turtoi and Nicolau, 2007). A salient feature of this non-thermal plasma technology is the ability to establish plasma inside a sealed package. This approach is referred to as the “in-package plasma” technology and has a striking parallelism with that of canning and HPP in that the plasma treatment is carried out inside a sealed package. Some cases of in-package decontamination are mentioned in Table 4.
Non thermal plasma technology is very much effective in decontamination of packaging materials as well. Packaging material sterilization is very important as it can ensure the stability of the stored product directly. Some findings about package sterilization of cold plasma technology is mentioned in Table 5.
Reducing enzymatic activities
Enzymes are naturally found in fresh fruits and vegetables. Polyphenoloxidase (PPO) and peroxidase (POD) are the two enzymes that are needed to be inhibited or inactivated so as to avoid undesirable browning reactions. The browning reaction also leads to the loss of sensorial or nutritional quality of fruits and vegetables. Some findings about enzymatic activities reduction potential of cold plasma technology is illustrated in Table 6.
Bio-film penetration capabilities
Biofilms are specialized structure of tightly grouped masses of microorganisms which are usually clustered together in complex extracellular polymeric substances excreted by the bacterial communities. The sole purpose is protection and to provide a water impermeable cellular protection. As soon as a bacterium gets attached to the food surfaces, it starts extracting nutrients and continues to reproduce and proliferate in the form of “biofilms”. Bacterial biofilms which gets developed in food and food processing surfaces germinates later on and leads to bacterial rot and affects the overall food’s quality and safety. The free radical liberated during the plasma treatment eventually penetrates the bacterial biofilms and leads to destruction of the hibernating bacteria.
Abramzon et al., (2006) applied RF high pressure cold plasma on
Chromobacterium violaceum in polystyrene microplates and observed that there was 100% cell death on 10 minute plasma treatment of 100 W.
Abbaszadeh et al., (2018) evaluated the effect of non-thermal plasma Technology (7 KHz for 0, 1 and 5 minutes) on quality preservation of fresh fig fruit both in packed and unpacked condition. Results shows a significant shelf life improvement for the treated figs compared to that of the control samples. Direct application of plasma for 90 s and in-package treatment for 30 s was suggested for further researches.
Modification of food properties
Cold atmospheric pressure plasma (CAPP) ensures a dynamic approach for systematic modification of food product properties along value-added chains of plant and animal related products. A prominent recent advances within the evolution of non-thermal food processing technologies is the feasibility of cold plasma for the enhancement of food properties
(Misra et al., 2016). Some findings about modification of food properties are mentioned in Table 7.
Insecticide and fungicide dissipation
Insecticides and fungicides are chemical compounds which are extensively used in modern agriculture to control pests. However these chemicals have some residual effects on the crops that are being consumed. Some findings about insecticide and fungicide dissipation utilizing cold plasma technology is mentioned in Table 8.
Other uses of non-thermal plasma technology
Fluorescent light bulbs/tubes
Fluorescent light bulbs works with the principle of plasma technology in which electric energy is converted to light energy. In a fluorescent lamp, there is a fluorescent tube that contains inert gas in very low pressure. An electric current in the plasma chamber excites the electrons. This produces a short wavelength of ultraviolet light. The phosphor coating inside the tube glows like a lamp.
Plasma TV display
A plasma television contains a plasma display panel containing several small plasma cells. These plasma cells have plasma matter present inside it. This plasma gets ionized in presence of the electric field.
Waste water treatment
Plasma technology can be effectively used for total purification and decontamination of waste water. Plasma technology is also known to remove colours and off odours from water. In present era, huge amount of water is contaminated with microbes, oils and deadly dye. These colours do not decompose and persist in system flora and fauna. Plasma technology is known to degrade dye including azo derivatives, anthraquinonoid, indigoid,
etc.
Rowan et al., (2007) performed pulsed plasma gas discharge (PPGD) on poultry wash water containing
Escherichia coli,
Campylobacter jejuni,
Campylobacter coli,
Listeria monocytogenes and
Salmonella spp. at 4°C. It was observed that there were 8 log reductions of bacteria and their spores.
Hand dryers
Cold plasma technology found its application as hand disinfecting agent along with drying of the palm. In developed countries, hand dryers are a part of culture in offices, institution, schools and household. In developing countries, it has application in executive hotels, elite household and executive government offices. It’s a part of sanitation movement which not only reduce water wastage but also help to ensure public hygiene. This technology is best suited to neutralize microbes including
Staphylococcus aureus, Salmonella sp.,
E.coli, norovirus and virus that cause influenza with a success percentage of 99.6% (
Anonymous 2018).
Advantages of cold plasma technology
Cold plasma technology is a very worthy technique for the enhancement of shelf life of fresh horticultural produce, cereals, pulses, food and dairy products. Following are the advantages of cold plasma technology:
a. This technique is feasible with all form of matter (solid, liquid and gases).
b. This process ensures a better decontamination of packaging materials without affecting its structure and barrier properties.
c. The products which are modified packaged can also be treated with plasma technology. Microbial inactivation of food products is very effectively done without any sort of heat treatment. Usually the thermally processed foods have a significant nutrient loss and reduction in organoleptic properties
(Sampedro et al., 2005). Application of non-thermal technologies is very effective at ambient temperature and minimizes all the adverse effects of heat treatment
(Tiwari et al., 2009).
d. Products decontaminated by this process tend to be more microbial stable.
e.
Bio-film penetration efficiency
Non thermal plasma technology can successfully get rid of microorganisms that harbour and perpetuate inside bio-films
(Critzer et al., 2007). Biofilms are big problems in case of fresh fruits, vegetables, dairy, poultry and meat industry (
Jessen and Lammert, 2003). Microorganisms are often found embedded in nutrient-rich environment of biofilms inside which they proliferate naturally without any external stress
(Vleugels et al., 2005; Simões et al., 2010).
f. This process can help to reduce the use of chemical preservatives.
g. Cold plasma does not leave any sort of residue in the treated food.
h. Treatment using cold plasma techniques would also help to minimize fresh water usage.
i. Cold plasma is much cost and energy efficient as its energy expenditure is like a 50 watt bulb.
Limitations of cold plasma technology
Like every other thing in our nature, the process of cold plasma technology also has some limitations. The limitations are listed below:
a. The process eventually increases the acidity and firmness of the treated food product which is not always desirable.
b. It is known to slightly reduce the colour of fresh fruits and vegetables slightly.
c. In products containing fat on the surface, plasma treatment can cause lipid oxidation and off-flavour.
d. The entire systems of cold plasma technology have a high installation cost and need a significant amount of technical know-how.
e. Penetration depth is very less in case of plasma technology.
f. The system seems to be non-feasible in Indian agriculture and horticulture system as far as cost is concerned.