Vijay Rakesh Reddy, S.
Ph.D. (PHT)
Roll No. 10183
Pesticide Residues & Food Safety
Ozone as an effective tool
Generation of ozone
Mechanism of action
Other Beneficial effects
Safety aspects of ozone & its by-products
Case studies (1-5)
Conclusion
Use of Pesticides-inevitable
to sustain food production
Pesticide consumption in India
increasing @ 2-5 % per annum
Synthetic pesticide are popular
easy application, quick result &
high economic return
IPM
pesticides as imp. component
Maximum Residue Limits (MRLs) :
codex alimentarious commission
Safe waiting period
after application of pesticides
Nanofiltration (Chen et al., 2004),
Activated carbon filtration (Foo and Hameed, 2010),
Reverse osmosis (Bonne et al., 2000),
Distillation (Gupta et al., 2006) ,
Adsorption (Tepus et al., 2009),
Photocatalytic degradation (Devipriya and Yesodharan, 2005),
Photodegradation (Tanaka and Reddy, 2002),
Ionising irradiation (Lepine, 1991),
Biodenitrification reactors (Aslan and Turkman, 2006),
Electrolysis adsorption (Vlyssides et al., 2005),
Microwaving (Salvador et al., 2002),
Electrochemical oxidation (Arapoglou et al., 2003) and
Ozonation (Ikeura et al., 2011)
Indian Agricultural Research Institute, New Delhi
A meta-stable molecule
Rapid auto-decomposition to diatomic O2
Pale blue (gaseous form);
Dark blue (liquid form)
Christian Friedrich Schnbein (Discoverer, 1840)
readily detectable by human nose at 0.01 to 0.04 ppm
Lethal at concentrations > 4 ppm
Indian Agricultural Research Institute, New Delhi
Involves passage of oxygen containing gas through either a
source of UV radiation or a high energy electrical field.
3O22O3 (H at 1 atm, +284.5 kJ/mol)
Various methods of generation include
Photochemical (UV) method
Corona Discharge / Plasma technique
Electrolysis method
Radiochemical method
Reaction of elemental Phosphorus with water etc.
Indian Agricultural Research Institute, New Delhi
Indian Agricultural Research Institute, New Delhi
Physical methods - measuring ozone properties (Intensity of
absorption in the UV, visible, or infrared region of the spectrum)
Physicochemical methods - measure effects of ozone reaction by
reagents (chemiluminescence or heat).
Chemical methods - quantity of the reaction products - released
when ozone reacts with an reagent (e.g., KI or HI)
- Indigo colorimetric method (Bader and Hoigne, 1981)
Sensitivity and accuracy varies by methods.
Accurate determination of gaseous ozone - UV spectrophotometric
method
Indian Agricultural Research Institute, New Delhi
In general, pesticide degradation can occur
biologically (i.e. microbial activity)
chemically (i.e. oxidation, reduction, hydrolysis, photolysis)
Ozone degrade chemical pesticides through oxidation
Being unstable in both gaseous phase and in solution, ozone
decomposes to hydroxyl (HO),
hydroperoxy (HO2) and
superoxide radicals (O2-)
The oxidizing power of these free radicals contribute to its high
reactivity.
They breakdown the chemical structure of pesticides and convert
them to CO2, water and other harmless products.
Advanced oxidation process-combined use of oxidants (O3+H2O2;
O3+UV).
Indian Agricultural Research Institute, New Delhi
Broad spectrum of anti-microbial activity
Surface disinfection of fresh produce
Sterilization of processed foods (juices etc.)
Barrel sanitizer in wine industry
Delay ripening of climacteric fruits (ethylene oxidation)
Sanitization of processing equipments (CIP)
Disinfection of municipal and process water
Sterilization of drinking water
Treatment of swimming pools
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Excess ozone decomposes rapidly to produce oxygen and this
leaves no residue in foods from its decomposition.
ozone produces no after-effects
It doesnt produce any detrimental chemical-organic reactions
Over exposure may cause ozone toxicity symptoms some
times (Headache, Dizziness, eye & throat infection etc.)
Indian Agricultural Research Institute, New Delhi
Sl No.
Crop
Pesticides
Ozone treatment
Effect on residues
References
Citrus
Chloropyrifos ethyl,
Tetradifon and
Chlorothalonil
Ozonated water (5, 6 and 10
ppm) for 5 min.
chlorothalonil & chloropyrifos
ethyl residues were removed
completely
Kusvuran et al.,
2012
2.
Baby corn
Chloropyrifos
Ozone gas & Ozonated water
(200 mg/L ) for 15, 30, 45
and 60 min
Ozonated water was more
effective than ozone gas in
degrading chloropyrifos
Whangchai, et
al., 2010
3.
Grape
Pyrimethanil, Iprodione,
Boscalid, Fenhexamid,
Cyprodinil
Ozone gas (0.3 L/L )
accelerated the decline of
fenhexamid , cyprodinil and
pyrimethanil
Karaca et al.,
2012
4.
Pak Choi
Diazinon, Methylparathion Ozonated water (1.4 and 2.0
Parathion, Cypermethrin mg/L)
Significantly degraded the
pesticides within 30 min.
Wu et al., 2007
5.
Chinese
white
cabbage &
Pak Choi
Permethrin
Chlorfluazuron
Chlorothalonil
Ozonated water (250 and
500 mg/h)
removal efficiency increased
with ozone production rate
and treatment duration
Chen et al.,2013
6.
Lettuce,
Cherry
tomato and
Strawberry
Fenitrothion
Ozone Micro Bubbles (2ppm
for 2 min)
The decompression type was
more effective than the gas
water circulation type
Ikeura et al.,
2011
Indian Agricultural Research Institute, New Delhi
Effect of continuous 0.3L/L gaseous ozone
exposure on fungicide residues on table grape berries
Karaca et al., 2012
Postharvest Biology and Technology, 64: 154-159
Objective:
To investigate the persistence of the residues of some common
vineyard fungicides
Treatments:
0.3 L/L ozone gas
Materials & Methods:
Grapes cv. Thompson Seedless
Pyrimethanil (37.1 g/L)
Iprodione (0.5 mL/L)
Boscalid (0.11 g/L)
Fenhexamid (0.29 g/L)
Cyprodinil (0.27 g/L)
Storage atmosphere (2C; 95% RH)
Sampling- 12 d interval
Residue analysis- GC-MS
Table 1. Persistence of residues (mg/kg) of fungicides iprodione, boscalid, fenhexamid,
cyprodinil, or pyrimethanil during the cold storage at 2C of Thompson Seedless table grape
berries in air or 0.3 L/L ozone, or after a single exposure to 10,000 L/L ozone fumigation for 1
h at 5C Ruby Seedless.
3.6 fold
The grapes were treated with the fungicides before ozone exposure.
Each value is the mean of three replicates
Indian Agricultural Research Institute, New Delhi
Under normal atmosphere, all other fungicides declined
significantly (%) except cyprodinil during 36 d storage period.
Ozone atmosphere storage accelerated the decline of
fenhexamid (1.6 fold), cyprodinil (2.8 fold) and pyrimethanil
(3.6 fold) but not of boscalid/ iprodione.
The low-dose and long-time ozone treatments are more
effective than high-dose and short-time treatments.
Indian Agricultural Research Institute, New Delhi
Removal of residual pesticides on vegetable using
ozonated water
Wu et al., 2007
Food Control, 18: 466-472
Objective:
To study the residual pesticide oxidation
To identify the ozonation byproducts tentatively using GC-MS
Treatments:
Ozonated water (1.4 and 2.0 mg/L)
Treatment temperatures (14 and 24C)
Treatment time (15 and 30 min)
Materials & Methods:
Pak Choi (Brassica rapa)
Diazinon (2 ppm for 2 min.)
Methylparathion (2 ppm for 2 min.)
Parathion (2 ppm for 2 min.)
Cypermethrin (2 ppm for 2 min.)
Residue analysis- GC-MS
99 %
60 %
Fig.1. The degradation of selected pesticides in 1.4 ppm ozonated water
Indian Agricultural Research Institute, New Delhi
Fig.2. Parathion degradation and paraoxon formation in the ozonation
process
Indian Agricultural Research Institute, New Delhi
Table 1. Pesticide levels and removal after rinsing vegetable with tap water and ozonated
water at 24C
Indian Agricultural Research Institute, New Delhi
Table 2. Residual pesticide after rinsing in 2.0 mg/L ozonated water at 14 and 24C
Indian Agricultural Research Institute, New Delhi
Methylparathion (60 %) and Diazinon (99 %) are significantly degraded by
ozonated water within 30 min.
Pesticide removal efficiency
-with 1.4 mg/L O3 for 15 min : 27-34 %
-with 2.0 mg/L of O3 for 15 min : 30-54 % and
-with 2.0 mg/L of O3 for 30 min : 45-61 %
The pesticide reduction efficiency of diazinon, Met.parathion, parathion and
cypermethrin increased from 36.2 %, 24.8 %, 19.7 % and 44.3 % at 14C
to 53.4 %, 47.9 %, 55.3 % and 61.4 % at 24C
Although parathion and diazinon produced trace amounts of oxons by ozone
oxidization, they were unstable in ozonation process.
Pesticide residue removal from vegetables
by ozonation
Chen et al., 2013
Journal of Food Engineering, 81: 404-411
Objective:
To develop a novel domestic-scale ozone cleaner
To establish relative conc. curves for liq. O3 conc. & ORP
To determine the efficiency of proposed ozone vegetable
cleaner in removing pesticide residues.
Treatments:
Ozonated water (250 and 500 mg/h)
Treatment duration (15, 30 and 45 min.)
Materials & Methods:
Chinese white cabbage and green-stem Pak Choi
Permethrin
Chlorfluazuron
Chlorothalonil
Indian Agricultural Research Institute, New Delhi
1. Cleaning chamber; 2. Chamber cover; 3. Vegetable basket; 4. Recirculation pump
5. Recirculation pipe; 6. Ozone generator ; 7. Ozone discharge tube; 8. Vent
Fig.1 Experimental setup of the pesticide residue cleaning machine
Table 1. Ozone treatment of aqueous pesticide solution (250 mg/h)
Table 2. Ozone treatment of aqueous pesticide solution (500 mg/h)
Indian Agricultural Research Institute, New Delhi
Pesticide removal efficiency improved with in ozone production rate and
treatment duration
The proposed ozone vegetable cleaner removed > 50% of these pesticides with
water recirculation for 15 min.
Removal efficiency for pesticide residue increased after adding ozone treatment
with an ozone production rate
at O3 production rate (250 mg/h) for 15 min, :
increased by about 10%.
at O3 production rate (500 mg/h) for 15 min, :
increased by about 30 %
When ozone production rate was increased
- removal efficiency of the proposed cleaner was 18.3% better than soaking alone.
Indian Agricultural Research Institute, New Delhi
Removal of residual pesticide, fenitrothion, in
vegetables by using ozone microbubbles generated
by different methods
Ikeura et al., 2011
Journal of Food Engineering, 103: 345-349
Objective:
To compare the efficiency of OMB (ozone micro bubbles)
generated by different methods in removal of pesticide residues
Treatments:
(A) Decompression type OMB generator (2 ppm O3)
(B) Gas-water circulating type OMB generator (2 ppm O3)
Materials & Methods:
Lettuce, Cherry tomato and Strawberry
Fenitrothion (500 ppm)
Ozone treatment time (0, 5 or 10 min.)
Fenitrothion
Fig. 1. GC-chromatogram of fenitrothion and d6-fenitrothion before and after
OMB treatments. (A) Before ozone treatment and (B) after ozone treatment
Indian Agricultural Research Institute, New Delhi
Fig. 2. Change in the DO3 concentrations after OMB treatments by using the gas
water circulating-type and the decompression-type.
Vertical bars represent the standard division of the mean (n = 3).
Different letters indicate a difference significant at the 5% level by TurkeyKramer
test between treatments.
Fig. 3. Residual fenitrothion percentages for lettuce (A), cherry tomatoes (B) and strawberries (C)
after immersion in solutions containing OMB generated by using the gaswater circulating-type
and the decompression-type..
Vertical bars represent the standard division of the mean (n = 3).
Different letters indicate a difference significant at the 5% level by TurkeyKramer test between treatments
Table 1. Concentration of residual FT for lettuce, cherry tomatoes, and strawberries after
immersion in solutions containing OMB generated by using the gaswater circulating-type
and the decompression-type.
72 %
74 %
19 %
21 %
26 %
46 %
Indian Agricultural Research Institute, New Delhi
In lettuce, the residual FT percentage was
- 44% and 55% after 5 min in the decompression type and the gaswater circulation type and
- 33% and 45% after 10 min. respectively
In cherry tomato, the residual FT percentage was
- 89% and 97% after 5 min in the decompression type and the gaswater circulation type and
- 84% and 95%, after 10 min. respectively
In strawberry, the residual FT percentage was
- 78% and 97% after 5 min in the decompression type and the gaswater circulation type and
- 62% and 87 %,after 10 min. respectively
Thus the decompression type was more effective than the gaswater circulation type because
of the larger number of small OMB that could more easily infiltrate into vegetables
Indian Agricultural Research Institute, New Delhi
Influence of fumigation with high concentrations of
ozone gas on postharvest gray mold and fungicide
residues on table grapes
Gabler et al., 2010
Postharvest Biology & Technology, 55: 85-90
Objective:
To evaluate the effect of single application of high dose O3
during pre-cooling to control postharvest decay
To study the role of O3 on field applied fungicide residues
Treatments:
Control
Gaseous ozone (0, 2500, 5000 or 10,000 L/L)
Materials & Methods:
Grape cv. Thompson Seedless, Red Globe, Autumn Seedless,
Black Seedless, Ruby Seedless
Cyprodinil (0.27 g/L)
Iprodione (0.5 mL/L)
Boscalid (0.11 g/L)
Fenhexamid (0.29 g/L)
Pyrimethanil (37.1 g/L)
Pyraclostrobin (0.06 g/L)
Thompson Seedless
Red Globe
Fig. 1. Gray mold incidence among inoculated Thompson Seedless and Red
Globe grapes that were fumigated in perforated cluster bags for 1 h with different
ozone (ozone) concentrations.
Fig.2. Occasional injuries to Thompson Seedless grape cluster rachis after grapes were
fumigated once with 5000LL1 ozone for 1 h. Grapes were stored for 7 d at 15C.
Table 1. Influence of 10,000LL1 ozone fumigation for 1 h at 5 C of Ruby Seedless table
grapes on residues (mg kg1) of fungicides applied before treatment.
Fumigation with 5000 L/L O3 for 60 min, gray mold incidence by
- approx. 50% in Autumn Seedless and Black Seedless table grapes,
- approx. 65% among Red globe table grapes.
Residues of fenhexamid, cyprodinil, pyrimethanil, and pyraclostrobin
were reduced by 68.5, 75.4, 83.7, and 100.0 %, respectively, after a
single fumigation of table grapes with 10,000 L/L ozone for 1 h.
However, residues of iprodione and boscalid were not significantly
reduced.
Indian Agricultural Research Institute, New Delhi
The low-dose and long-time ozone treatments are more effective than highdose and short-time treatments.
The O3 water degraded organophosphates (60-99 %) in 30 min and the
ozonation byproducts -unstable in O3 environment.
The ozonated water recirculation - increased the removal efficiency by 10 and
30 % at 250 and 500 mg/h of O3 production.
The decompression type OMB generator > effective than the gaswater
circulation type
Fumigation of grapes with 10,000 L/L for 1 hr completely eliminated the
fungicide pyraclostrobin.
Indian Agricultural Research Institute, New Delhi
Since the ozone dosage, treatment time and temperature could
impact the efficiency in pesticide removal, these parameters
should be optimized for different fruits and vegetables.
Research should be focused on development of improved
devices for O3 gas production
Should investigate the feasibility of direct production of O3
containing water without prior production of O3 gas
Indian Agricultural Research Institute, New Delhi
