application of ozone for removal of pesticide residues from fruits & vegetables

8/9/2019 Application of ozone for removal of pesticide residues from fruits & Vegetables

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Vijay Rakesh Reddy, S.Ph.D. (PHT)

Roll No. 10183


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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


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•

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


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• 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


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•

A meta-stable molecule• Rapid auto-decomposition to diatomic O 2

• Pale blue (gaseous form);

• Dark blue (liquid form)

• Christian Friedrich Schönbein (Discoverer, 1840)

•

readily detectable by human nose at 0.01 to 0.04 ppm• Lethal at concentrations > 4 ppm



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• Involves passage of oxygen containing gas through either a

source of UV radiation or a high energy electrical field.

3O 2↔2O 3 (ΔH° 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.



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Broad spectrum of anti-microbial activitySurface disinfection of fresh produceSterilization of processed foods (juices etc.)Barrel sanitizer in wine industryDelay 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 doesn’t produce any detrimental chemical -organic reactions

Over exposure may cause ozone toxicity symptoms some

times (Headache, Dizziness, eye & throat infection etc.)



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Sl No. Crop Pesticides Ozone treatment Effect on residues References

1 Citrus Chloropyrifos ethyl,Tetradifon and

Chlorothalonil

Ozonated water (5, 6 and 10ppm) for 5 min.

chlorothalonil & chloropyrifosethyl residues were removed

completely

Kusvuran et al.,2012

2. Baby corn Chloropyrifos Ozone gas & Ozonated water(200 mg/L ) for 15, 30, 45and 60 min

Ozonated water was moreeffective than ozone gas indegrading chloropyrifos

Whangchai, etal., 2010

3. Grape Pyrimethanil, Iprodione,Boscalid, Fenhexamid,Cyprodinil

Ozone gas (0.3μ L/L ) accelerated the decline offenhexamid , cyprodinil andpyrimethanil

Karaca et al.,2012

4. Pak Choi Diazinon, MethylparathionParathion, Cypermethrin

Ozonated water (1.4 and 2.0mg/L)

Significantly degraded thepesticides within 30 min.

Wu et al., 2007

5. Chinesewhitecabbage &Pak Choi

PermethrinChlorfluazuronChlorothalonil

Ozonated water (250 and500 mg/h)

removal efficiency increasedwith ozone production rateand treatment duration

Chen et al.,2013

6. Lettuce,Cherrytomato andStrawberry

Fenitrothion Ozone Micro Bubbles (2ppmfor 2 min)

The decompression type wasmore effective than the gas–water circulation type

Ikeura et al.,2011



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Effect of continuous 0.3 μL/L gaseous ozoneexposure on fungicide residues on table grape berries

Karaca et al ., 2012

Postharvest Biology and Technology, 64: 154-159


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↓3.6 fold

Table 1. Persistence of residues (mg/kg) of fungicides iprodione, boscalid, fenhexamid,cyprodinil, or pyrimethanil during the cold storage at 2 °C 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 1h at 5 °C ‘Ruby Seedless’.

• The grapes were treated with the fungicides before ozone exposure.• Each value is the mean of three replicates



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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.



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Wu et al ., 2007

Food Control, 18: 466-472

Removal of residual pesticides on vegetable usingozonated water


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Objective :To study the residual pesticide oxidationTo identify the ozonation byproducts tentatively using GC-MS

Treatments:Ozonated water (1.4 and 2.0 mg/L)Treatment temperatures (14 and 24 °C)

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


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60 %

99 %

Fig.1. The degradation of selected pesticides in 1.4 ppm ozonated water



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Fig.2. Parathion degradation and paraoxon formation in the ozonation process



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Table 1. Pesticide levels and removal after rinsing vegetable with tap water and ozonatedwater at 24 °C



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Table 2. Residual pesticide after rinsing in 2.0 mg/L ozonated water at 14 and 24 °C



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• Methylparathion (60 %) and Diazinon (99 %) are significantly degraded by

ozonated water within 30 min.• Pesticide removal efficiency

-with 1.4 mg/L O 3 for 15 min : 27-34 %

-with 2.0 mg/L of O3

for 15 min : 30-54 % and

-with 2.0 mg/L of O 3 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 14 °C

to 53.4 %, 47.9 %, 55.3 % and 61.4 % at 24 °C

• Although parathion and diazinon produced trace amounts of oxons by ozone

oxidization, they were unstable in ozonation process.


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Pesticide residue removal from vegetables by ozonation

Chen et al ., 2013

Journal of Food Engineering, 81: 404-411


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Objective :To develop a novel domestic-scale ozone cleaner

To establish relative conc. curves for liq. O 3 conc. & ORPTo determine the efficiency of proposed ozone vegetablecleaner 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

PermethrinChlorfluazuronChlorothalonil



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1. Cleaning chamber; 2. Chamber cover; 3. Vegetable basket; 4. Recirculation pump5. Recirculation pipe; 6. Ozone generator ; 7. Ozone discharge tube; 8. Vent

Fig.1 Experimental setup of the pesticide residue cleaning machine


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Table 1. Ozone treatment of aqueous pesticide solution (250 mg/h)

Table 2. Ozone treatment of aqueous pesticide solution (500 mg/h)



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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 treatmentwith an ozone production rate

– at O 3 production rate (250 mg/h ) for 15 min, : increased by about 10%.

– at O 3 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.



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Ikeura et al ., 2011

Journal of Food Engineering, 103: 345-349

Removal of residual pesticide, fenitrothion, invegetables by using ozone microbubbles generated

by different methods


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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 O 3)(B) Gas-water circulating type OMB generator (2 ppm O 3)

Materials & Methods:Lettuce, Cherry tomato and Strawberry

Fenitrothion (500 ppm)

Ozone treatment time (0, 5 or 10 min.) Fenitrothion


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Fig. 1. GC-chromatogram of fenitrothion and d6-fenitrothion before and afterOMB treatments. (A) Before ozone treatment and (B) after ozone treatment



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Fig. 3. Residual fenitrothion percentages for lettuce (A), cherry tomatoes (B) and strawberries (C)after immersion in solutions containing OMB generated by using the gas – water circulating-typeand 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 Turkey – Kramer test between treatments


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Table 1. Concentration of residual FT for lettuce, cherry tomatoes, and strawberries after

immersion in solutions containing OMB generated by using the gas – water circulating-typeand the decompression-type.

74 %

21 %

46 %

72 %

19 %

26 %



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• In lettuce, the residual FT percentage was

- 44% and 55% after 5 min in the decompression type and the gas – water 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 gas – water 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 gas – water circulation type and

- 62% and 87 %,after 10 min. respectively• Thus the decompression type was more effective than the gas – water circulation type because

of the larger number of small OMB that could more easily infiltrate into vegetables



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Objective :To evaluate the effect of single application of high dose O 3during pre-cooling to control postharvest decay

To study the role of O 3 on field applied fungicide residuesTreatments:ControlGaseous ozone (0, 2500, 5000 or 10,000 μL/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)

Th S dl Red Globe


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Fig. 1. Gray mold incidence among inoculated ‘Thompson Seedless’ and ‘RedGlobe’ grapes that were fumigated in perforated cluster bags for 1 h with differentozone (ozone) concentrations.

Thompson Seedless Red Globe


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Fig.2. Occasional injuries to ‘Thompson Seedless’ grape cluster rachis after grapes werefumigated once with 5000 LL− 1 ozone for 1 h. Grapes were stored for 7 d at 15 ◦C.

Table 1. Influence of 10,000LL −1 ozone fumigation for 1 h at 5 ◦C of ‘Ruby Seedless’ tablegrapes on residues (mg kg− 1) of fungicides applied before treatment.


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• Fumigation with 5000 μL/L O 3 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 μL/L ozone for 1 h .

• However, residues of iprodione and boscalid were not significantly

reduced.



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• The low-dose and long-time ozone treatments are more effective than high-

dose and short-time treatments.

• The O 3 water degraded organophosphates (60-99 %) in 30 min and the

ozonation byproducts -unstable in O 3 environment.

•

The ozonated water recirculation - increased the removal efficiency by 10 and30 % at 250 and 500 mg/h of O 3 production.

• The decompression type OMB generator > effective than the gas – water

circulation type

• Fumigation of grapes with 10,000 μL/L for 1 hr completely eliminated the

fungicide pyraclostrobin.



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• 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 O 3 gas production

• Should investigate the feasibility of direct production of O 3

containing water without prior production of O 3 gas



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application of ozone for removal of pesticide residues from fruits & vegetables

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