Gavahian 2021

Food Research International 141 (2021) 110138
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Food Research International

journal homepage: www.elsevier.com/locate/foodres
Cold plasma for mitigating agrochemical and pesticide residue in food and
water: Similarities with ozone and ultraviolet technologies
Mohsen Gavahian a, *, Chaitanya Sarangapani b, N.N. Misra c
a
Department of Food Science, National Pingtung University of Science and Technology, Pingtung 91201, Taiwan, ROC
b
School of Food Science and Environmental health, Technological University Dublin, Dublin, Ireland
c
Department of Engineering, Faculty of Agriculture, Dalhousie University, Nova Scotia, Canada
A R T I C L E I N F O A B S T R A C T
Keywords: Pesticide and agrochemical residues in food and water are among hazardous chemicals that are associated with
Plasma adverse health effects. Consequently, technologies for pesticide abatement in food and water remain in focus.
Pesticide residue Cold plasma is an emerging decontamination technology, that is being increasingly explored for the abatement of
Ultraviolet
agrochemical and pesticide residue in food and water. In some cases, rapid and complete degradation of pesticide
Ozone
Emerging processing technologies
residues has come to light. Such promising results encourage exploring scale-up and commercialization. To
achieve this, unraveling mechanisms involved in plasma decontamination and the nature of degradation prod
ucts is needed. The present review identifies the mechanisms involved in plasma- assisted removal of pesticide
residues from food and water, draws parallels with mechanism of ozone and ultraviolet technologies, investigates
the chemistry of the intermediates and degradates, and identifies some future research needs. The review rec
ognizes that mechanisms involved in plasma processes have overlapping similarities to those identified for ozone
and ultraviolet light, involving oxidation by hydroxyl radical and photo-oxidation. The toxicity of intermediates
and degradates in plasma processing have not received much attention. The safety aspects of end products form
plasma led degradation of pesticides should be considered for practical exploitation. Identification of in
termediates and degradation products, recognition of most potent plasma species, understanding the influence of
co-existing entities, the energy efficiency of plasma reactors, and the process economics deserve research focus.
1. Introduction growth of unwanted plants or weeds responsible for interrupting the

growth of crops or damaging the agricultural product (Nardemir et al.,
The contamination of a variety of food and agricultural products 2015). This category of pesticides has a high consumption rate in many
with pesticide and other agrochemical residues is continuing to rise as a countries such as the United States (Fig. 2). The third category of pes
global challenge (Böhme et al., 2018; Prodhan et al., 2016, 2018; Tong ticides, i.e., “other pesticides”, includes insect repellents, arsenical,
et al., 2018; Xiao et al., 2019). This is due to the high volumes of fungicides, fumigants, rodenticides, and some other items (EPA, 2018).
application of agrochemicals, such as pesticides, around the world for Health issues associated with the consumption of pesticide residues
meeting the productivity demands (Fig. 1). Pesticides are substances, vary based on exposure time, individual health condition, type of
with a variety of chemical structures, that are utilized for pest control pesticide, etc. and include reproductive system disorder, neurological
(Razzaghi et al., 2018; Svingen et al., 2018). According to the United consequences, skin disorders, visual disruption, paralysis, and cancer
States Environmental Protection Agency (US-EPA) (EPA, 2018), pesti (Debnath & Khan, 2017; Valcke et al., 2017).
cides are categorized as insecticides, herbicides, and other pesticides. Due to the health and environmental concerns, the concentration of
Insecticides are defined as substances intended for killing the closely pesticide residues in food commodities is limited by regulatory bodies
related group of insect species (Guedes et al., 2017). Pyrethrins and via establishing limits for pesticide residues in various foods. Also,
pyrethroids, organophosphate insecticides, n-methylcarbamate, and regulatory bodies across the world banned the use of several low-cost
organochlorines are examples of insecticides (Shrestha et al., 2019). environmentally persistent pesticides such as dichlorodiphenyltri
Herbicides are described as crop-protecting chemicals that inhibit the chloroethane and hexachlorocyclohexane. Moreover, reducing the use
* Corresponding author.
E-mail address: mohsengavahian@yahoo.com (M. Gavahian).
https://doi.org/10.1016/j.foodres.2021.110138
Received 25 July 2020; Received in revised form 6 January 2021; Accepted 7 January 2021
Available online 18 January 2021
0963-9969/© 2021 Elsevier Ltd. All rights reserved.
M. Gavahian et al. Food Research International 141 (2021) 110138
of these chemicals are among the sustainable development goals (SDGs). markets are contaminated with health-threatening agrochemcial resi
Regardless of these efforts, pesticides are still popular in many devel dues (Dixit et al., 2019; Shrestha et al., 2019; Taiwo, 2019). This
oping countries as reported in the literature (Carvalho, 2006; Pallarés necessitate the removal of pesticide residue from food commodities
et al., 2020; Sheikha, 2015). before consumption.
Chemical-free agriculture and organic farming have been suggested Washing, chemical sanitization with chlorine-based compounds and
as possible solution by some researchers but these types of farming are thermal processing are probably the most common traditional practices
unlikely to meet the human demand for food (Jouzi et al., 2017). aiding pesticide removal from food commodities. Many of the pesticides
Therefore, using pesticides, especially in tropical regions of the world, is are water-insoluble (e.g. hexachlorocyclohexane and endosulfan) which
still a common practice and many of the food commodities available in makes washing only a partially reliable technique for pesticide
Fig. 1. The use of pesticide in different regions of the world in 2014. The data are presented as average pesticide application per unit of cropland, measured in km per
hectare (a); and the annual use of pesticide (×1012 kg) in major pesticide consumer countries (b) (Max & Ritchie, 2019).
2
elimination (Fuentes et al., 2018). In addition, recent studies have occurring over various length and time scales (Misra et al., 2018). The
suggested that chemical sanitization could generate several carcino similarities between cold plasma and these technologies in terms of
genic by-products, which has even led to the prohibition of chemical chemical compositions and mode of actions make it interesting to
washing in many regions of the world (Phan et al., 2018). In some cases, compare the efficacy of pesticide degradation by these non-thermal
harsh thermal treatments can ensure a pesticide-free product but these techniques to assess their prospective commercial applications.
may negatively affect their physicochemical, nutritive and organoleptic Furthermore, there is limited information regarding the safety of the
properties (Heo et al., 2014). Therefore, researchers are exploring non- degraded products of pesticides after plasma treatments, and hence,
thermal advanced oxidation approaches for removing pesticide residues those knowledge gaps need to be addressed. Therefore, this review
from agricultural products (Gavahian & Cullen, 2020; Gavahian & discusses the recent findings with regards to the efficacy of cold plasma
Khaneghah, 2020). An overview of the nonthermal and advanced in pesticide degradation in comparison with ozone and ultraviolet pro
oxidation technologies as used for dissipation of pesticides on food cesses. Besides, the mechanisms involved and the safety of plasma-
products is provided in an earlier work (Misra, 2015). The purpose of generated degradants in pesticide removal processes are discussed.
this review is to specifically focus on the growing area of plasma tech Finally, future trends and the research needed in this area of science are
nology for mitigating the problem of agrochemical residues in foods. highlighted.
Plasma is essentially an ionized gas that is electrically quasi-neutral.
Plasma consists of reactive species (e.g. ions, free electrons, atoms, and 2. Pesticide degradation by cold plasma
photons) in the ground or excited states that are characterized by a
neutrality of the net charge. The term “cold” in the context of plasma The applicability of plasma technology for the degradation of many
refers to the near ambient temperature of the overall gas, despite the agrochemical residues in food and water is being increasingly investi
electrons being several 1000 ◦ K hot (Gavahian, Chu, et al., 2019; Sar gated. Some of the commonly studied agrochemicals include cyprodinil,
angapani et al., 2018). Microbial decontamination is the widely omethoate, dichlorvos, fludioxonil, parathion, azoxystrobin, paraoxon,
researched application of cold plasma for food commodities (Gavahian, and pyriproxyfen (Table 1). That said, in general, there is only limited
Peng, et al., 2019; Gavahian, Sheu, et al., 2020). However, research data available in the literature regarding the removal of agrochemical
pertinent to other applications, including the degradation of pesticide residues from fruits and vegetables (Phan et al., 2018). It should note
residues in food and water is also increasing. This application is based on that cold plamsa technology can mainly dissipate agrochemical residues
the hypothesis that plasma generated reactive species in the air (e.g. H+, from the surface of the product which should be considered while dis
H− , O+, O− , H3O+, OH− , H2O2, N+ 2 , O2, N2, O3, OH , NO , O , H etc.)
• • • •
cussing the overall performance of such a process. What follows next is a
can attack the pesticide molecules and alter/degrade the health- discussion of the salient findings from these studies.
hazardous molecules (Misra et al., 2019; Pankaj et al., 2018; Sar More than a decade ago, the effects of atmospheric pressure cold
angapani et al., 2016). Indeed, research findings corroborate this hy plasma on paraoxon and parathion were studied, which verified the high
pothesis and confirm the applicability of this emerging technology for efficacy of this technology for the degradation of pesticides dispersed on
the degradation of pesticides (Phan et al., 2018; Sarangapani et al., the surface of a glass slide (Kim et al., 2007). It was noted that OH,
2017). The presence of a relatively high concentration of ozone (O3) and oxygen atoms, and N2 were among the main reactive species of cold
ultraviolet (UV) photons in plasma, in many cases, makes it closely plasma that affected paraoxon and parathion. Later, it was reported that
related to ozone and UV processes which have been well-explored as a 120 W inductively coupled plasma applied for 2 min removed almost
nonthermal pesticide degradation approaches (Vasseghian et al., 2020). all the dichlorvos and omethoate from corn surface (Bai et al., 2009).
A summary of the recent studies in this area of reseatch is presented in Subsequently, complete degradation of malathion that was placed on
Table 2. For example, the effect of O3 on dissipation of pesticide residue the surface of filter papers in about seven minutes was observed using a
is documented in a previously published paper (Pandiselvam et al., plasma jet (Zhu et al., 2010). According to Zhu et al. (2010), this
2020). However, cold plasma is complex and unique with the involve decontamination process involved oxidation of P = S bond and cleaving
ment of over one hundred reactive species and thousands of reactions the P–S and S–C bonds. The plasma-induced oxidation, which was
Fig. 2. Pesticide breakdown by type in the United States (Max &Ritchie, 2019).
3
Table 1
Recently conducted studies on the application of cold plasma for the removal of agrochemicals residues.
Agrichemical residue Maximum Treated Sample/ Treatment conditions Main observations Reference
degradation Sample size
(%)
Malathion 64.6 Water/2 mL Atmospheric air DBD plasma; Voltage: 60, 70, Degradation efficiency was directly (Cong et al.,
Chloropyrifos 62.7 80 kV; Treatment time: 30, 60, 90, 120, 150, correlated with applied voltage and 2020)
180 s; Initial concentration: malathion (0.1, treatment time
0.5 and 2.5 μg/mL) and chlorpyrifos (0.2, 1.0
and 5.0 μg/mL)
Carbaryl 50.5 Water/20 mL Atmospheric air DBD plasma; Voltage: 70, 80, Degradation was lowest in case of (Moutiq et al.,
Methiocarb 99.6 and 90 kV; Treatment time: 60, 120, 180, 240, carbaryl. The ROS and RNS were 2020)
Aminocarb 99.3 300 s; Initial concentration: 20 mg/kg for all responsible for degradation. Most
pesticides degradates were found to be less toxic than
parent molecule.
Organophosphorus 99.5 Diazinone Atmospheric air microplasma system at an The degradation efficiency depended on (Khan et al.,
(diazinone) dissolved in average power of 154 W/h the concentration of plasma-generated 2020)
methanol/20 mL reactive species.
Oxides of nitrogen and ozone were
considered as the most important and the
second most important species in
degradation of diazinone, respectively.
The degradation of diazinone followed a
1st order kinetics.
Phoxim 74 Water/400 mL 600 W gliding arc plasma with argon gas as the The oxidation capacity and acidic (Zheng et al.,
carrier environment of PAW were effective in 2019)
degrading phoxim
Alachlor 80 Water/60 mL DBD system operated at input voltage of 80 kV, Degradation occurred mainly via (Wardenier,
frequency 50 kHz for 0–30 min oxidation mechanism involving O3 and Gorbanev, et al.,
OH radical 2019)
Malathion 59.0 Lettuce/NA Voltage: 80 kV; Treatment time: 30, 60, 90, The degradation efficacy on lettuce is Cong et al.
Chloropyrifos 57.9 120, 150, 180 s; Initial concentration: 0.5 mg/ lower than in water. The color and (2020)
kg for malathion and 1.0 mg/kg for chlorophyll of lettuce was not significantly
chlorpyrifos affected. Vitamin C content decreased
Dichlorvos 96.8 Wolfberry/NA Discharge plasma (gas phase surface type) Performance of plasma in pesticide (Zhou et al.,
Omethoate 99.6 Voltages of 5–15 kV for 0.5–30 min removal depended on applied voltage and 2018)
treatment time.
Cypermethrin 63 Mango/1 fruit Gliding arc discharge system Plasma was shown to be effective for (Phan et al.,
Chlorpyrifos 74 Argon was the carrier gas agrochemical removal from mango 2018)
surface
Boscalid 75 Blueberries/100 In-package atmospheric DBD plasma Pesticide degradation was mediated by (Sarangapani
Imidacloprid 80 g 60–80 kV for 2–5 min reactive species generated et al., 2017)
Dichlorvos 78 Water/20 mL In-package plasma generated from Pesticide degradation was depended on (Sarangapani
Malathion 69 a DBD system structure of pesticides. et al., 2016)
Endosulfan 57 Input voltage was 60 to 80 kV for 1–8 min
* DBD: Dielectric barrier discharge; PAW: Plasma-activated water; NA: Not available.
comprehensively discussed in a previous study, should be considered 74% and 63% reduction in the concentrations of chlorpyrifos and
when analyzing the mechanisms of pesticide degradation by plasma cypermethrin after a relatively short treatment time of five minutes.
(Gavahian et al., 2018). In another investigation, 96% of paraoxon was They also observed a reduction in total phenolic content and acidity, an
removed from the surface of apple fruits by using a DBD plasma source increase in the percentage of carotenoid, and no significant changes in
(Heo et al., 2014). Misra et al. (2014) evaluated the possibility of mango’s color, texture, total soluble solids. In another study, surface
chemical decontamination of strawberries spiked with pesticides (Misra discharge plasma was employed to remove organophosphorus pesticides
et al., 2014). They showed that in-package gas-phase plasma treatment viz. dichlorvos and omethoate, from wolfberry (Zhou et al., 2018). This
plasma can effectively reduce the concentration of various agrochemical investigation revealed that the processing time and input voltage gov
residues including cyprodinil, azoxystrobin, pyriproxyfen, and fludiox erned the efficiency of the system and the highest dissipation was
onil. These researchers reported that the applied voltage and process observed at 10 kV for a processing time of half an hour, resulting in
duration had a direct relationship with the dissipation of agrochemicals, dichlorvos and omethoate reduction by about 97% and 100%, respec
with the highest dissipation observed at an input voltage of 80 kV and 5 tively. These authors also claimed that the degraded products were safe
min treatment time. Under these process conditions, 71% of fludioxonil, as evidenced through toxicity studies involving luminosity reduction of
69% of azoxystrobin, 46% of pyriproxyfen, and 45% of cyprodinil were a probe bacterium (Vibrio fischeri). Interestingly, the reactive species and
degraded. The author reported that plasma treatment did not signifi energetic electrons responsible for pesticide dissipation did not
cantly alter the quality parameters of the product which made the adversely affect the quality parameters of the wolfberry. Furthermore,
plasma technology suitable as an intervention tool for pesticide abate researchers recently explored the effects of DBD argon plasma on the
ment. In a more recent study, cold plasma was also shown to be effective removal of carbaryl and chlorpyrifos residues from the surface of maize.
in degrading organophosphorus residues in cucumbers and apples They documented that the highest carbaryl and chlorpyrifos degrada
(Mousavi et al., 2016). tion rates were 73.1% and 91.5%, respectively (Feng et al., 2019).
A recent investigation explored the applicability of a gliding arc Moreover, a research team investigated the applicability of 4–6 min of a
discharge system with argon (as the carrier gas) for decontamination of 2–5 W DBD plasma for treatment of tomatoes which contained 0.6–0.8
mango samples contaminated by chlorpyrifos and cypermethrin at mg/kg chlorpyrifos residue. This research team reported that the 6 min
laboratory-scale, i.e., one mango was immersed into one liter of distilled of 5 W DBD treatment was responsible for about 89.2% reduction in the
water in each treatment (Phan et al., 2018). The authors documented chlorpyrifos concentration which was the greatest reduction value
4
Table 2
M. Gavahian et al.
A summary of the recent studies on the respective reductions of pesticides on fresh produce and water involving gaseous or aqueous ozone and UV light.
Pesticide Max. degradation (%) Treated Sample Treatment conditions Main observations Reference
Fenitrothion 32 Lettuce Aqueous O3 microbubble O3 microbubble process did not no significantly affect color and (Ikeura et al., 2011)
52 Cherry tomatoes process (2 mg/kg for 20 min) pulling strength
at 30 ℃
Chlorfenapyr 92 Tomatoes Gaseous O3 process of 2 mg/ Residues of chlorfenapyr were reduced by 88% at ozone (Al-Antary et al., 2019)
kg for 15 min concentration of 0.5 mg/kg with increase in ozone concentration
to 2 mg/kg reduced chlorfenapyr by 92%
Chlorpyrifos 53 Spinach Washing in 0.4 mg/l O3 Degradation of pesticides depends on surface area (Wang et al., 2019)
Myclobutanil 72 solution for 0.5 h
Tebuconazole 73
Bifenthrin 62
Beta-cypermethrin 63
Lamda-cyhalothrin 67
Esfenvalerate 78
Difenoconazole 68
Acetamiprid 64
Imidacloprid 63
Myclobutanil 99 Lettuce leaves Aqueous O3 treatment (0.5, 2, Ozone affected the pesticides (Al-Dabbas et al., 2018)
5 mg/kg) for 5, 10 and 15 min residues concentration in a concentration–time dependent
manner.
Difenoconazole 98 Carrots 5 mg/l and 10 mg/l O3 gas Process efficiency parameters were optimized for ozone (Souza et al., 2018)
Linuron 95 treatments using central composite design
Deltamethrin 85 Wheat grains O3 gas treatment at Relationship between humidity and pesticide degradation. (Savi et al., 2015)
89 concentration of (60 µmol/ Higher humidity treatment showed maximum pesticide
mol) for 180 min degradation
Captan 38 Raspberries Drying of fruits using Ozone drying process potentially increased the effectiveness of (Balawejder et al., 2014)
58 Blackcurrants ozonation pesticide removal.
5
UV light
Trichlorfon 67 Virgin olive oil A 150 W immersion system of Pesticide degradation was dependent on the process (Nieto et al., 2009)
Parathion methyl 79 photochemical (200–280 nm) temperature and time (15–30 ◦ C)
Parathion Ethyl 74
Diuron 76
Chlorpyrifos 65
Simazine 43
Chlorpyrifos methyl 61
Terbutryn 44
Malathion 49
Metidathion 30
Endosulfan I 11
Pirimiphos methyl 9
Fenitrothion 9
Chlorpyrifos 71 Apple UV-C (254 nm) lamp at 65 kJ/ Degradation of chlorpyrifos was mainly related to the dose of (Ho et al., 2020)
Food Research International 141 (2021) 110138

m2, power 25 W UV-C and temperature
Atrazine 34 Water UV-C (254 nm) lamp (Power Degradation of Atrazine was mediated by hydroxyl radicals (Moreira et al., 2017)
15 W) treatment for 300 s
Dichlorvos 50 Water UV irradiation of deionized Dichlorvos degradation combines direct photocleavage and (Bustos et al., 2019)
and ultra-pure water for 24 h photo-induced ROS generation when submitted to UV-C (254
using multiple UV lamps nm) irradiation
(power 4 W and 8 W)
Diazinon 52 Water Power 9 W UV lamp light A 2nd kinetic model used tp describe photolysis oxidation (Jafari et al., 2016)
intensity 2.2 mW/cm2 for 30 pattern of diazinon
min
obtained in their study. The GC–MS assay revealed that 3,5,6-trichloro (Sarangapani et al., 2017). For instance, the cold plasma generated using
pyridinol (TCP) was a principal metabolite of chlorpyrifos degrada air as a discharge gas produces active species, such as O3 (E0 = 2.1 V),
tion. Such an observation is related to plasma chemistry, considering the OH• (E0 = 2.8 V), and H2O2 (E0 = 1.8 V), that have high oxidation
high concentration of free radicals and reactive species in plasma which potentials (Misra, Schlüter, et al., 2016). The concentration of ozone
can degrade chlorpyrifos into smaller components and reduce its con varies widely depending on the process conditions. It is generally re
centration (Ranjitha Gracy et al., 2019). In a recent study, researchers ported to be between 101 to 103 mg/kg (Feizollahi et al., 2020). Simi
demonstrated the possibility of breaking down carbamate pesticides in larly, the lifetime could vary between 10 and 30 min, depending on the
water using an atmospheric pressure DBD plasma source at 70–90 kV, temperature, and presence of other molecules (McClurkin-Moore et al.,
50 Hz, and 1–5 min treatment duration (Moutiq et al., 2020). They 2017). Such potent species disassociate the pesticide molecule and often
attributed the degradation to the reactive oxygen and nitrogen species resulting in pesticide degradation. Also, the UV light (typically emitted
formed in the plasma, as identified through emission spectroscopy. between 200 and 350 nm wavelength) and shock waves generated
Further, they also noticed that the extent of degradation varied during the plasma process are also believed to contribute to pesticide
depending on the pesticide, even though these belong to the same degradation.
chemical class. For example, the extent of degradation was much lower Ozone produced during plasma treatment acts as a powerful oxidant,
for carbaryl as compared to methiocarb and aminocarb, despite all of specifically measured as one of the stable products in air plasma
them belonging to the carbamate class of pesticides. discharge, thereby also rendering itself to ease of quantification (Sar
All the studies discussed so far point at the highly effective action of angapani et al., 2016). Ozone generation at industrial scales involves
the active plasma species on pesticide residues. A general conclusion electrical discharges in oxygen or air from a corona or DBD plasma
that can be drawn from the survey is that the efficacy of decontamina source. The electron impact dissociation of the oxygen molecule results
tion can be enhanced through process optimization involving selection in a singlet oxygen. The recombination of this singlet oxygen with mo
of appropriate plasma source and process conditions such as process lecular oxygen results in ozone formation (Misra et al., 2016). Several
duration, applied voltage, and carrier gas composition. authors have reported effective degradation of pesticide residues in
fruits and vegetables using oxygen plasma in the gaseous or aqueous
3. Mechanistic insights for action of plasma on pesticides medium (Heleno et al., 2014; Kırış & Velioglu, 2015; Souza et al., 2018).
The mechanism of oxygen plasma led degradation of pesticides involves
A closer look into the plasma chemistry, such as the composition of direct oxidation by oxygen atoms and ozone, while indirect oxidation is
reactive species, could provide a better understanding of the mecha mediated by hydroxyl radicals. Pesticide degradation in water occurs via
nisms of plasma led dissipation of pesticides (Sarangapani et al., 2016). photolysis, hydrolysis and oxidation–reduction reactions (Chamberlain
The energy of electrons in plasma processes is typically about 10 eV et al., 2012). Ozone generated during oxygen plasma disrupts the un
when it used for food processing. Hence, components with similar saturated aliphatic moieties by oxidative cleavage, thereby substantially
ionization energy might be affected in such a process (Bai et al., 2010; changing the molecular structure of the pesticides and causing them to
Misra et al., 2016). In other words, pesticide molecules might be directly lose their potency. Direct oxidation by ozone of dichlorovinyl, nitro,
affected by plasma. Plasma reactive species (e.g. ozone, hydroxyl methoxy, amino and other functional groups of pesticide results in the
radical, and hydrogen peroxide) influence the pesticide molecules production of small-molecule compounds such as acids, alcohols,
through oxidation reactions (Bai et al., 2009, 2010). At the same time, amines, and carbonyls (Qiao et al., 2012). These small molecule com
the effects of UV emission on molecules should also be considered as pounds are primarily water-soluble which can be washed away with tap
described in a previous study (Tsao & Eto, 1994). Also, most of the water resulting in products with reduced amounts of chemical residues.
plasma processes operate at a relatively low temperature of around 40 Bai et al. (2010) proposed two pathways for degradation of dichlorvos
◦
C. In this sense, plasma can be considered as a non-thermal, quick, and by oxygen plasma including addition reaction and free radical reaction.
physicochemical approach for pesticide removal which is not associated They recognized that the degradation product 2,2-dichlorovinyl O-
with the production of secondary pollutants (Bai et al., 2009, 2010). methylphosphate formed via free radicals attack where as other two
Zhou et al. (2018) proposed two possible pathways for plasma-induced intermediates O,O,O-trimethyl phosphoric acid and O,O-dimethly
pesticide degradation which were discussed in detail in an earlier work phosphonic ester required both free radical and electron interactions
(Gavahian & Khaneghah, 2020). It should be noted that the exact as presented in Fig. 3. Likewise, it was proposed that radical and electron
mechanism should be determined for each pesticide in a specific food/ impact mediated processes could result in degradation of diazinon on
water matrix when treating with a specific plasma source, and under cucumber by air-DBD plasma (Dorraki et al., 2016). The degradation of
predefined process conditions. In this regard, important data is reported diazinon molecule involved attacks by ROS causing hydrogen abstrac
in previous research which revealed that energy fed to electrons and free tion of the CH3O and removal of CH2O, leading to the generation of
radicals are the major parameters governing the plasma-induced “degradation product # 2” as shown in Fig. 4. Electron impact on the
degradation of dichlorvos and organophosphorus while hydroxyl radi diazinon molecule and transfer of electron energy results in the forma
cals were found to be effective in removing dimethoate (Bai et al., 2009, tion of “degradation product # 3 and # 4”.
2010; Hu et al., 2013; Misra, Pankaj, et al., 2016; Zhu et al., 2010). It The efficiency of plasma processing for degradation of agrochemical
was also reported that the attack of hydroxyl radicals to the double residues depends on many factors such as applied voltage, treatment
bonds of P = S are major mechanisms in decontamination of dimethoate duration, discharge gas used, type of food (substrate), class of pesticide
which is accomplished by oxidation of omethoate to C3 and C2 products and concentration of pesticide residue. In-package DBD plasma pro
through hydroxyl radical attack. These chemical reactions are followed cessing of strawberries spiked with a cocktail of pesticides (azox
by P-S bonds cleavage and release of N-methyl acetamide groups (Hu ystrobin, cyprodinil, fludioxinil and pyriproxyfen) showed that the rate
et al., 2013). of pesticide dissipation reduced when longer processing times were
The electron impact dissociation during plasma treatment leads to a applied (Misra et al., 2014). These authors also identified the dominance
variety of physicochemical effects (e.g. the primary formation of of ozone in reaction pathways of pesticide degradation. The significance
oxidizing species: radicals (H•, O•,OH•) and molecules (H2O2, O3, etc.), of pesticide structure on degradation by plasma was also emphasized by
ultraviolet light and occasionally, depending on the process, shock Sarangapani et al. (2016). They reported that the removal efficiencies of
waves) (Jiang et al., 2014). The presence of these reactive species is a organophosphorus (malathion and dichlorvos) were higher in compar
process that underlines its effects on pesticides. The formation of highly ison with organochlorine (endosulfan) due to differences in the elec
active species depends on the configuration of the plasma reactor, e.g. tronegativities and bond energies. The lower bond energies of P-S in
electrode properties, structure of the reactor and the gas input malathion and P-O in dichlorvos contribute to highest degradation
6
Fig. 3. Proposed reaction pathways for malathion oxidation by plasma adapted from Magureanu, et al., (2018), Sarangapani et al. (2016), and Zhu, et al., (2010).
Fig. 4. Proposed reaction pathways for Diazinon oxidation by plasma as reported by Dorraki, et al., (2016). The reactions involved radical and electron impact
mediated degradation.
7
efficacies to that of endosulfan which consists of S = O with higher bond plasma-activated water (PAW) in removal of phoxim residues on grapes
energy. These authors have also reported the formation of intermediate (Zheng et al., 2019). They suggested that the phoxim concentration
and degradation products. The reaction pathways involved the first reduced with time considered for PAW preparation. The maximum
steps of oxidation of P-S, P-O and P = S by hydroxyl radicals leading to reduction of phoxim achieved was 73% after 10 min treatment with
the formation of malaoxon. The breakdown of C-S leads to the formation PAW-30 (PAW treated for 30 min). These authors have identified in
of main intermediate products such as succinic acid, O,O,S-trimethyl termediate products and proposed the possible degradation pathway of
phophoro dithioate and diethyl fumarate. Similar products were also phoxim after PAW treatment. The reaction pathway followed was
detected by Zhu et al. (2010) who employed an atmospheric pressure similar to that of other organophosphorus pesticides such as malathion,
radiofrequency He/oxygen plasma jet for degradation of malathion. parathion containing S = P, where oxidation species destroy S = P by the
Furthermore, photolysis of malathion also resulted in phosphorodithioic subsequent opening of N-O to form other products. The detailed
O,O,S-trimethyl ester and phosphorothioic O,O,S-trimethyl ester as degradation pathway of phoxim was proposed by a group of researchers
major intermediate compounds and diethyl (dimethoxy-phosphoryl) who investigated photocatalytic degradation of phoxim over La-doped
succinate in traces (Bavcon Kralj et al., 2007). In another study, re TiO2 nanoparticles in aqueous solution (Dai et al., 2009).
searchers observed differences in removal efficiencies of chlorpyrifos Plasma technology has successfully demonstrated its potential in the
(74%) and cypermethrin (62%) sprayed on mango surface by gliding-arc treatment of potable water and wastewater effluent from the food in
discharge plasma (Phan et al., 2018). This is because, ozone, one of the dustry. Generally, ozone and hydroxyl radical generated during plasma
major active species in plasma is relatively less effective against pyre treatment play an important role in the degradation of organic mole
throid when compared to organophospate. Likewise, a research team cules in water (Sarangapani, 2019). The mechanism of plasma degra
employed a low-pressure non-thermal DBD plasma for chlorpyrifos dation of pesticides can be either by direct or indirect oxidation by
reduction on tomatoes (Ranjitha Gracy et al., 2019). These authors converting hydroxyl radicals (Pisarenko et al., 2015). The direct reac
proposed chlorpyrifos degradation was primarily dependent on plasma tion takes place in acidic environments, while at high pH indirect is
doses and treatment time. The plasma-induced degradation of chlor predominant. Nevertheless, both reactions could occur simultaneously
pyrifos involved substitution reactions with phosphoryl group (P = O) to to oxidize the pesticide. The electron dissociation of water molecules
produce chlorpyrifos oxon. Further oxidation of chlorpyrifos oxon also leads to the formation of hydroxyl radical which further recombines
dissociated into fragments of diethyl phosphoric acid and 3,5,6-trichlor to form hydrogen peroxide in water (Sarangapani et al., 2019). The
opyridinol. Similar fragments were also identified as degradation reactive nitrogen species generated during air–water plasma treatment
products of chlorpyrifos upon ozonation (ElMasri et al., 2014), UV- can also react with pesticides and generate new compounds through
photolysis and UV/H2O2 (Ho et al., 2020). chemical processes such as nitration and nitrosation (Lukes et al., 2012).
The efficiency of pesticide degradation by plasma is also related to The degradation mechanism of pesticides carbofuran and 2,4-
the surface area and properties of the food matrix. Mousavi et al. (2016) dichlorophenoxyacetic acid (2,4-D) using a pulsed corona discharge
documented the relationship between the effects of cold plasma degra above water was carried out in a previous study (Singh et al., 2016). The
dation and the structure of tissues. These authors emphasized that oxidation of pesticides is attributed to •OH radical attack to form car
diazinon and chlorpyrifos residues are easier to remove from apples than bamic acid from carbofuran and 2–4-dichlorphenol from 2 to 4-D. The
cucumbers. This is owing to the thin layer of skin on apples making the dominant degradation pathway follows dissociation of C-O bond on the
reactive species penetrate easily leading to more oxidation when benzene by •OH as a result of hydroxylation. Several other oxidation
compared to that of cucumber. In addition to the thickness of fruit skin, routes involve, hydroxylation of aromatic/furan moieties (with/without
fruit surface roughness can be considered as an effective parameter for Cl substitution) suggesting a ROS mediated mechanism followed by
this observation. Similarly, it has been recently reported that the low demethylation. The subsequent oxidation of alkyl group leads to the
degradation rates by ozonation in cucumber and kumquat when formation of hydroxylated benzenes. Further addition of •OH to double
compared to spinach are due to its lesser surface area (Wu et al., 2019). bond, and finally, ring opening with the formation of carboxylic acids.
Pesticide degradation by plasma treatment on leafy vegetables is often From the reaction pathway a generalized plasma degradation pathway
considered to be more efficient than fruits, due to the thick pericarp in of carbofuran and 2,4-D was proposed previously which is presented in
fruits making it difficult for the reactive species to penetrate the cuticle Fig. 5 (Magureanu et al., 2018). Similar degradation products were also
and reach the center (Wang et al., 2019). Another research group identified by researchers who treated 2,4-D in aqueous solution using a
applied ozone gas generated by corona discharge plasma technology at planar falling film DBD reactor in different gas atmospheres, that is,
60 µmol/mol during the wheat grains storage at variosu moisture con argon, argon + oxygen or air (Aziz et al., 2018). These authors detected
tent (Savi et al., 2015). The authors found that the pesticides in higher intermediate compounds such as glycoxylic and oxalic acids to be most
humidity (20% moisture with aw 0.9) were degraded at higher rates resistant to plasma treatment (Jiang et al., 2014).
when compared to that of stored at lower moisture contents (12% More recently, Khan et al. (2020) elucidated the mechanisms
moisture with aw 0.6). This shows that humidity also plays an important involved in the plasma-induced degradation of diazinone (Fig. 6). These
role in realizing the efficiency of ozone/plasma degradation. This is in authors showed that plasma treatment results in the oxidation of dia
agreement with other studies where the plasma chemistry was found to zinone upon interaction with major plasma-produced compounds to
be far more effective in the humid air as compared to dry air (Moiseev breakdown into smaller molecular fragments. Besides, the authors
et al., 2014; Patil et al., 2014). The degradation of boscalid and imida explained that progressive degradation happened in this decontamina
cloprid on blueberries by atmospheric air plasma was investigated by tion process. Also, it was revealed that various radicals that are available
Sarangapani et al. (2017). The maximum reductions observed after 5 in the plasma discharge water have various roles in diazinone degra
min of plasma exposure at 80 kV was found to be 75% for boscalid and dation. The degradation mechanism of diazinone followed, hydroxyl
80% imidacloprid (Sarangapani et al., 2017). They suggested the ation to form hydroxy diazinone, these hydroxylated compounds
degradation of these two pesticides followed different mechanisms. The undergoes a dehydration reaction to form isopropenyl derivative.
mechanism of degradation involved direct attacks of hydroxyl radicals Further oxidation and decarboxylation of diazinone derivative resulted
on benzene and pyridine rings of boscalid leading to the formation of in generation of hydroxyethyl derivative. These authors have also
hydroxylated products and other carboxylic acids. Similarly, degrada concluded that intermediate products formed were less toxic than the
tion of imidacloprid involved hydroxylation to form 6-chlornicotinic parent compounds. The oxides of nitrogen played a key role in the
acid. Similar degraded products were also identified in photocatalytic degradation process while they acknowledged that ozone is the second
degradation of boscalid and imidacloprid (Lagunas-Allué et al., 2010; most important species among other plasma-generated reactive species.
Malato et al., 2001). Recently, researchers investigated the efficacy of Interestingly, this study revealed that H2O2 played a minimal or no
8
Fig. 5. Generalized pathway for the degradation of Carbofuran and 2,4-D by plasma. The reactions involve several mechanisms including oxidation, reduction and
hydrolysis. Adapted from Magureanu et al. (2018) and Singh et al. (2016).
9
Fig. 6. Possible mechanisms involved in diazinone degradation by a cold plasma process and the proposed structures of the fragments according to Khan et al (2020).
The reactions include a variety of mechanisms including oxidation, hydroxylation and hydrolysis in aqueous medium.
significant role in the degradation of diazinone (Khan et al., 2020). determination. Herein, we have provided examples of simple ap
As a general observation, it may be noted that the degradation proaches for the first-hand exploration of the toxicity of end products
products identified after plasma treatment were also identified in ozo after plasma degradation, as evidenced from literature. We hope that
nated, UV, UV/O3, UV/H2O2 and other advanced oxidation processes these will inspire future studies and allow to obtain a good picture of the
(AOPs). This showed that there are some degree of overlap in the action toxicity of the end-products.
of DBD plasma, ozonation and other AOP treatments, involving ozone One straightforward approach for assessing the toxicity of trans
and hydroxyl radical as main oxidizing species (Magureanu et al., 2018). formation products would be to compare their Lethal dose (LD50) values
Despite their short lifetime, reactive nitrogen species being capable of obtained from literature against the parent pesticide. The LD50 is the
lowering the pH during plasma processing are also important. Finally, quantity of an ingested substance that kills 50 percent of a test popu
ozone often plays a crucial role in the removal of many pesticide mol lation. The LD50 values are expressed as the amount of the substance per
ecules (Heleno et al., 2014; Jiang et al., 2014; Pandiselvam et al., 2020). kg body weight of the organism. Based on the oral LD50 value, a sub
The degradation of organic compounds by plasma treatment generates stance is classified under high toxicity (less than 50 mg/kg), moderate
several intermediates. In some cases, the toxicity and recalcitrance of toxicity (50–500 mg/kg), low toxicity (500–5000 mg/kg) or very low
these new chemical compounds could exceed the toxicity and recalci toxicity (>5000 mg/kg) (EPA, 2018). The toxicity of intermediates and
trance of the parent molecule. Therefore, it is important to address the end degradates after cold plasma treatment could be more, equal, or less
identification of transformation products and/or assess their toxicity. toxic compared to the parent molecule. To cite an example, dimethoate
pesticide on oxidation could transform to its oxo-analogue, omethoate
4. Toxicity of intermediates and degradation products which is more toxic. If the end degradate is more toxic than the parent
molecule, it does not serve the purpose of plasma treatment. However,
The changes in the chemical structure of the plasma-treated pesti further treatment using alternative technologies could be an option to
cides imply changes in the properties of the resulting transformation transform such end-products.
products, including their toxicity. The identification of transformation Another simple experimental approach to assess the toxicity of
products of a pesticide subjected to advanced oxidation processes and parent pesticides and their degradation products is to carry out the agar
their toxicity determination is often challenging due to the involvement disc-diffusion test. Herein, the parent pesticide and the solutions after
of several intermediates. The non-availability of commercial standards plasma treatment are spiked onto paper discs which are placed on agar
of many predicted degraded products also limits their toxicity plates with a model organism. The solution from the disc diffuses into
10
the agar and inhibits the growth of the organism. The diameter of the 5.2. Identification of most potent plasma species
inhibition zone is taken as a measure of the toxicity of the plasma-
treated solution. Recently, researchers evaluated the toxicity of chlo Plasma, as discussed earlier, comprises of several active species and
robenzene solution (a solvent used in agrochemical formulations) sub the degradation effects are predominantly attributed to ROS and RNS,
jected to pulsed plasma treatment, via disc diffusion test using E. coli and with a small contribution from UV photons and heat generated treat
found no zone of inhibition as compared to a 10 mm zone for untreated ment. It remains unclear as to which of these species are functional for
samples (Jose &Philip, 2019). This suggested that plasma treatment the degradation of specific pesticides. Identifying the order of func
resulted in a non-toxic product. tionality is important for exploring the mechanisms and maximizing the
An alternative study to assess the toxicity of breakdown products, pesticide degradation. While such information cannot be easily extrac
specifically for organophosporous pesticides, is to check their effect on ted through simple experiments, some empirical approaches could turn
acetylcholinesterase (AChE) enzyme activity using Ellman’s protocol out to be helpful. For example, when employing gas-phase plasma,
(Ellman et al., 1961; Lazarević-Pašti et al., 2016). Using the AChE assay, varying gas compositions could help answer the effect of ROS versus
it has been shown that plasma treatment of dimethoate spiked tap water RNS. The identification of the potent plasma species and the influence of
resulted in negligible toxicity after treatment. In another recent study, operating conditions can also be approximated using computer simu
the biological toxicity of plasma-treated pesticide cocktail mixtures lations of mathematical models. This is especially a good option when
spotted on aluminum plates and exposed a roller conveyor plasma treating whole fruits or vegetables. While such studies have not been
source was evaluated using AChE activity inhibition (Toyokawa et al., reported for the degradation of pesticides on food samples, learning
2018). The authors found that the DBD plasma operating at 10 kVp-p and from the modelling of soil remediation using plasma treatment can be
10 kHz frequency considerably decreased the AChE inhibition activity of extended as reported in a recent investigation (Bali et al., 2019).
the pesticide cocktail mixtures, PL-14–2 (containing more than 25 pes
ticides) and FA-2 (containing more than 20 pesticides), as observed 5.3. Influence of co-existing entities and surface features on degradation
through qualitative assay kits. Thus, these toxicity studies helped to efficiency
assess the effectiveness of plasma treatment from a biological standpoint
and future work should consider such experiments. The breakdown of pesticides using cold plasma technology is
Occasionally, it is possible that a longer treatment duration may be commonly reported in aqueous solutions of pesticides prepared in lab
necessary for transforming the pesticides into no-toxic products. It has oratories While such studies using pure water serve the purpose as a
been reported that a pulsed corona plasma discharge resulted in an in proof-of-concept, it is to be noted that pesticide pollutants are usually
crease in the toxicity of carbofuran solution up to 2 min duration, present in the soil, groundwater, wastewater effluents, and surface
whereas extending the treatment to 10 min resulted in complete water. Therefore, it remains unclear as to how the technology will
detoxification (Singh et al., 2016). The toxicity, in this case, was perform with the co-existence of ionic species, organic and non-organic
assessed against microalga Chlorella vulgaris. This group, later also re materials. Here, it is important to highlight that polar pesticide solutions
ported the detoxification of 2,4-D in 10 min using the same reactor are often prepared in methanol or ethanol and subsequently diluted
(Singh et al., 2017). using water for research trials. However, the alcoholic groups could
themselves quench and react with the active species of plasma. There
5. Future trends and research needs fore, further studies are required to understand the influence of the co-
existing chemical entities on the degradation efficacy. Likewise, it is also
5.1. Identification of intermediates and degradation products unclear if the nature of the surface of food or agricultural produce has an
influence on the pesticide breakdown on exposure to plasma. There have
In general, literature pertinent to cold plasma degradation of pesti been no studies to evaluate the influence of surface roughness of the
cides in food and water reveals that the focus has been to understand the produce, for example, to assess the difference between a tomato surface
degradation kinetics and the ability to reach below the maximum res versus a strawberry.
idue limit (MRL value). The mechanism of degradation is often specu
lated based on the findings of previously conducted studies on pesticide 5.4. The energy efficiency of plasma reactors
degradation during other decontamination approaches. The reason for
this gap can be attributed to the fact that identifying intermediates in In general, the energy efficiency of plasma reactors for chemical
degradation pathways demands the availability of commercial stan disinfection of food and water is a less researched and under-reported
dards of the intermediates and end degradates. However, high purity topic. The energy yield of different plasma reactors could vary consid
commercial standards are often unavailable or very expensive, thereby erably depending on the operating parameters such as the applied
limiting the analytical processes. One approach that could help to voltage, frequency, type of discharge, operating pressure, and the
overcome this limitation to some extent would be to employ state-of-the- presence of catalysts (Misra & Roopesh, 2019). At the same time, the
art analytical techniques (e.g. NMR spectroscopy). Further, in many extent of degradation could also vary significantly depending on the
cases, tracking the fate of the functional groups associated with a chemical structure of the pesticide, its concentration, by-products
pesticide could provide sufficiently useful information regarding their formed, pH, the gas used for plasma generation and so on (Malik,
toxicity. Where feasible, real-time monitoring of the functional groups 2010). Therefore, to get an estimate of the energy efficiency, calculation
using vibrational spectroscopy could also be an option, as was demon of the degradation per unit of energy measured in moles/J is suggested.
strated in the literature for the breakdown of cypermethrin by ozone and This index of efficiency is also regarded as the specific energy con
hydroxyl radicals (Segal-Rosenheimer et al., 2011; Segal-Rosenheimer sumption of the plasma reactor. An alternative approach to energy
&Dubowski, 2007). Recently, calculations based on Density Functional calculation in continuous treatment of water could be the use electrical
Theory (DFT) has also been employed as a useful tool to assess the energy per order (EE/O, kWh/m3), which represents the electrical en
reactive sites of dimethoate pesticides and its intermediates subjected to ergy input (kWh) required to reduce the initial pesticide concentration
plasma treatment (Mitrović et al., 2019). Functional groups in pesticides with 1 order of magnitude (90%), in 1 m3 of water (Equation (1))
are often related to their toxicity and tracking their fate during cold (Wardenier, Vanraes, et al., 2019).
plasma treatment could provide a valuable means to assess the toxicity
P
of the breakdown products relative to the parent molecule (Misra, EE/O = ( ) (1)
2015). f . CC0i
11
wherein P the total power dissipated in the reactor (kW), f is the water Furthermore, similar to ozone treatment and UV treatment, the possible
flow rate (m3h− 1), Ci and Cf represent the initial and final pesticide negative effects of plasma processing on the quality attributes of the
concentration (µgL-1 or molarity), respectively. This approach is also food should be considered. Obviously, not all the food materials are
suitable when using plasma-activated water for pesticide dissipation in suitable for plasma treatment for long durations (e.g. some foods with
fruits and vegetables (Zheng et al., 2019). In any case, the energy should high lipid content). Fortunately, several studies revealed that such
refer to the actual energy fed to the plasma discharge, so that the in negative changes are limited, and they could be further minimized
fluence of different power transformers or power converters can be through process optimization. Therefore, the unavailability of such in
eliminated from the picture. An assessment of the energy efficiency will formation is another limitation for the commercialization of cold plasma
also enable a direct comparison of the plasma technologies with other systems. These limitations should be addressed in future research.
relevant advanced oxidation technologies. For example, based on energy
expenditure calculations, a group of researchers reported that the 7. Conclusions
operating cost for N,N-dimethylformamide removal by DBD plasma is
relatively lower as compared to Fenton oxidation, wet oxidation, pho With the rising population of the world, the decrease in arable land
tocatalysis, and pulsed high voltage discharge (Sang et al., 2019). and climate change scenarios, there is a mounting pressure on global
Similarly, another group of researchers reported that the cost of pulsed agriculture to increase productivity. The use of pesticides and other
plasma-assisted degradation of chemical pollutants in water is lower as agrochemicals has become an integral part of modern industrialized
compared to ultrasonication alone or even in combination with UV (Jose agriculture and will continue to stay in practice, despite their known
&Philip, 2019). The higher energy efficiency of plasma as reported in deleterious health effects. One possible solution to tackle this issue is to
many cases could be due to the rapid formation of a myriad of reactive employ technologies that could considerably decrease and ideally,
species (thereby actuating multimodal action) at high concentrations eliminate the pesticide residues in food and water. Cold plasma is an
with low energy requirements. emerging nonthermal technology showing considerable promise for
such applications. Residues of several classes of pesticides have been
demonstrated to decrease in fruits, vegetables and water following the
5.5. Process optimization and mathematical approaches to enhance action of atmospheric and low-pressure plasma. The degradation action
plasma performance for pesticide reduction of plasma is a result of the action of a gamut of highly reactive species
generated in plasma discharges, that share some degree of overlap with
The development of empirical models could be useful to analyze the the action of other advanced oxidation processes (e.g. ozone and UV).
effects of processing parameters such as plasma source electrical pa The efficacy of the dissipation of pesticide residues is dictated by the
rameters and exposure time on the pesticide degradation trend. In this type of plasma source, as well as the process conditions, such as the
sense, Taguchi-grey theory and response surface methodology are applied voltage or power input, the type of gas, and the treatment
among the tools already explored for optimization of such processes (Al- duration. There exists considerable scope for optimization of the plasma
Hilphy et al., 2020; Al-Hilphy et al., 2020; Chung et al., 2020). However, process parameters for achieving higher efficacy of degradation and
once exact mechanisms will be available, dissipation kinetics can be elimination of pesticide residues. It is recommended that future studies
mechanistically modelled and analysed. should focus on the biological toxicity of end products of degradation for
practical use. Besides, evaluating the energy efficiency of the plasma
6. Limitations and considerations reactors and adding an economic lens for process evaluation will be
helpful to assess the scalability of plasma processes to commercial or
Notwithstanding the number of published papers in this area of household scales.
research, cold plasma is certainly an infant in the area of chemical
decontamination of food and water. Therefore, the shortcomings of this CRediT authorship contribution statement
technology deserve analysis and discussion to render commercial
feasibility. The main issue that needs to be highlighted is the scale of Mohsen Gavahian: Conceptualization, Writing - original draft,
previously conducted studies. Most of the references reviewed in the Methodology, Writing - review & editing, Visualization. Chaitanya
present work have been conducted at laboratory scales. Therefore, Sarangapani: Writing - original draft, Writing - review & editing,
upscaling studies are needed to provide information about the efficiency Visualization. N.N. Misra: Conceptualization, Writing - original draft,
of the plasma systems that can be used for the removal of agrochemical Methodology, Writing - review & editing, Supervision.
residues. Second, the cost of the plasma system should be considered. In
particular, an affordable and scalable plasma system will be much
appreciated by the agri-food industry. It should be noted that plasma Declaration of Competing Interest
chemistry varies depending on the plasma source and there is a need for
a comprehensive study to compare the capability of various plasma The authors declared that there is no conflict of interest.
equipment in terms of pesticide abatement ability, similar to that re
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