Pesticide Residues in Imported Fruits and Vegetables

PML/PR-39/2011

Pesticide Residues in Imported Fruits and Vegetables

INVESTIGATORS

Dr. Sapna Johnson

Mr. Ramakant Sahu

Mrs Poornima Saxena

ADVISORS

Prof. (Dr.) H. B. Mathur

Prof. (Dr.) H. C. Agarwal

DATE

December 2011

CENTRE FOR SCIENCE AND ENVIRONMENT

41, TUGHLAKABAD INSTITUTIONAL AREA, NEW DELHI –110062

PH: 91-11-2995 6110/5124/6394/6399

FAX: 91-11-2995 5879 EMAIL: [email protected]

WEBSITE: www.cseindia.org

POLLUTION MONITORING LABORATORY

INDIA HABITAT CENTER, CORE-6A, FOURTH FLOOR

LODHI ROAD, NEW DELHI – 110003

1. POLLUTION MONITORING LABORATORY OF CSE

The Centre for Science and Environment (CSE), a non-governmental organization based in New Delhi,

has set up the Pollution Monitoring Laboratory (PML) to monitor environmental pollution. PML is an ISO

9001:2000 certified laboratory accredited by SWISO, CH-5610, Wohlen, Switzerland, conducting

Pollution Monitoring and Scientific Studies on Environmental Samples. The Lab has highly qualified and

experienced staff that exercise Analytical Quality Control (AQC) and meticulously follow what is called

Good Laboratory Practices (GLP). It is equipped with most sophisticated state-of-the-art equipments for

monitoring and analysis of air, water and food contamination, including Gas Chromatograph with Mass

Detector (GC-MS), Gas Chromatograph (GC) with ECD, NPD, FID and other detectors, High

Performance Liquid Chromatograph (HPLC), Atomic Absorption Spectrometer (AAS), UV-VIS

Spectrophotometer, Mercury Analyzer, Respirable Dust Sampler etc. Its main aim is to undertake

scientific studies to generate public awareness about food, water and air contamination. It provides

scientific services at nominal cost to communities that cannot obtain scientific evidence against polluters

in their area. This is an effort to use science to achieve ecological security.

2. INTRODUCTION

In many agriculture areas, pesticides are used intensely. In these areas, fruits and vegetables are very

important, and therefore acaricides, insecticides, fungicides, and herbicides are applied on the

agriculture areas. Many different types of pesticides are used extensively, leading to the contamination of

pesticide residues in fruits and vegetables. Pyrethroid, organophosphorus and carbamate residues are

frequently detected in fruit and vegetable crops Fruit and vegetables usually receive direct application of

pesticides in the field or in post-harvest treatment and may retain a proportion as residues in or on the

edible portion delivered to the consumer [1]. Therefore, public concern about the contamination of food

by pesticides has been increasing over the past years due to the uncertainty about the adverse effect of

those residues may pose over a long-time exposure. The toxicity of most pesticides and the consumption

of raw fruit and vegetables reinforce the concern for contamination of these food substances over other

foods [2] . As a result, levels of pesticides in different food item are regulated by international and

national organizations in order to protect human health [3]. That is for the protection of the public against

the toxic effects of pesticides, regulatory agencies in many countries have established standards

specifying the residue levels of each pesticide in various foodstuffs. At an international level, the WHO, in

conjunction with the FAO, has been convening Joint FAO/WHO Meetings on Pesticide Residues

annually since 1961. [4].Almost every country either imports or exports food. Most countries do both [5].

According to the WorldHealth Organization (WHO), food consumption consists on average for 30%

(based on mass) of fruit and vegetables, and fruit andvegetables are the most frequently consumed food

group (WHO,2003).

Given the potential risk of pesticides for public health, the use of pesticides in agriculture is subjected to

constant monitoring. The surveillance focuses on the proper use of pesticides in terms of authorization

and registration (application rates and pre-harvested intervals), and on compliance with maximum residue

limits or MRLs. Although the surveillance output (detection frequency percentage of samples exceeding

the MRL) gives a good indication,it lacks the information necessary for a proper interpretation

andobjectification in terms of food safety. To evaluate the safety of

.A total of 7,905 samples of domestically produced food and imported food from 102 countries were

analyzed for pesticide residues in FY 2004. No residues were found in 58.6 % of domestic and 66.4 % of

import samples analyzed under FDA's regulatory monitoring approach in 2004. Violative residue levels

were found in 1.8 % of domestic and 5.5% of import samples. The findings for 2004 demonstrated that

pesticide residue levels in foods are generally well below EPA tolerances, corroborating results

presented in earlier reports FDA also collected and analyzed 476 domestic and 102 import animal feed

samples for pesticides. No residues were found in 74.4 % of the domestic feed samples and 78.4 % of

the import feed samples.( FDA Pesticide Program Residue Monitoring 2004-2006 March 16, 2011)

A total number of 11,610 samples of nine different commodities (oranges, mandarins, pears, potatoes,

carrots, cucumbers, spinach, beans without pods, and rice) were taken in the 2008 EU coordinated

pesticide monitoring programme. These samples analysed for 78 pesticides .2.2% of the samples

exceeded the MRL, while the percentage of samples with measurable residues above the quantification

level, but at or below the MRL, was 35.7%. In 62.1% of the samples no residues were detected. The

overall MRL exceedance rate was comparable with the previous year rate (2.3%). It is noted that the

percentage of samples without measurable residues increased from 52.7% in 2007 to 62.1% in 2008.

The highest percentage of samples exceeding the MRL was identified for spinach (6.2%) followed by

oranges (3.0%), rice (2.4%), cucumbers (2.1%), mandarins (2.0%), carrots (1.8%), pears (1.6%), beans

without pods (0.8%) and potatoes (0.5%).(EFSA,2008)

http://www.efsa.europa.eu/en/efsajournal/pub/1646.htm

As fruit and vegetables are mainly consumed raw or semi-processed, it is expected that they contain

higher pesticide residue levels compared to other food groups of plant origin, such as bread and other

foodstuffs based on cereal processing. In addition, it is well known that animal products are less

contaminated by currently registered agricultural pesticides. Pesticide residues can sometims exceed the

safe limits precrbed, therefore PML tested imported Fruits and Vegetable samples from different countries

US, Australia , New Zea Land Thailand, Italy France for the presence of organochlorine pesticides

residue(14), organophosphorus pesticide(11), synthetic pyrethroids(4) and carbamates(2) which could be

contaminated with pesticide residues. 16 different types of n fruits and vegetable samples obtained from

local food marketsof Delhi were investigated. 35b major types of pesticides( oragonochlorines,

pyrethroids,organophosphorus , and carbamates were analysed by standard methodology using gas

chromatography

3. Review of Literature

Fruits and Vegetables:

India is the second largest producer of vegetables after China, and accounts for 13.4% of world

production. Surveys carried out by institutions spread throughout the country indicate that 50-70% of

vegetables are contaminated with insecticide residues. Madan et al (1996) reported the presence of

monocrotophos, quinalphos, BHC isomers, DDT analogues and endosulfan in cauliflower, cabbage and

pea peel samples collected from different fields, located in the vicinity of Hissar, Haryana. Among all the

samples, only one sample of cabbage contained 0.23mg/kg of monocrotophos which was above the

MRL (0.2 mg/kg). In another study (Gupta et al., 1998), out of 27 samples of bottle gourd, 4 showed

monocrotophos residues in the range of 0.18-0.67 mg/kg, 3 samples were contaminated with fenvalerate,

2 each with endosulfan and phosphamidon and one each with HCH and DDVP. Cauliflower samples

were found contaminated with monocrotophos (0.12-1.5 g/gm), quinalphos (0.15-0.6 g/gm), dimethoate

(0.05-0.2 g/gm), chlorpyriphos (0.15 g/gm), fenvalerate (0.08-2.5 g/gm), endosulfan (0.05-2.5 g/gm)

and HCH (0.03-2.1 g/gm). Out of the 13 samples analysed, 4 samples showed monocrotophos residues

in the range of 0.2-1.17 g/gm, 4 samples showed endosulfan residues in the range of 0.04-3.0 g/gm. In

a study, done by Sanghi and Tewari (2001), it was clear that malathion was the most abundantly used

organophosphate pesticide for both fruits and vegetables. Higher concentration of malathion was found in

vegetables (0.024-3.74 mg/kg) compared to that of fruits (0.43-2.32 mg/kg). Residues of DDT, DDE,

BHC, dimethoate, endosulfan and ethion were also detected in a few samples. Presence of pesticide

residues in fruits and vegetables were also reported from Islamabad, Pakistan (Tahir et al., 2001).

Dimethoate was present in the quantity of 0.032mg/kg in apple, 0.110mg/kg in banana, 0.004mg/kg in

brinjal, 1.80mg/kg in cauliflower and 0.13mg/kg in arvi, fenvalerate 0.010mg/kg in apple and chlorpyriphos

0.004 mg/kg in brinjal.

Over 27,000 food samples were tested, and most were found to be within the established U.S. legal limits

for pesticides on those foods. The foods found to have the highest levels of pesticide residues were

domestic and imported peaches, grapes, apples, pears and spinach; U.S.-grown green beans; and U.S.-

grown winter squash, both fresh and frozen. Of these, peaches and frozen winter squash had the highest

residue quantities, about 10-fold higher than the other "high scores" according to the study. Foods with

the lowest levels of pesticide residues were frozen/canned corn, milk, U.S. orange juice, U.S. broccoli,

bananas and canned peaches. Slightly higher, but still within legal limits, were frozen/canned sweet peas,

U.S. and imported apple juice, Mexican frozen winter squash, Canadian tomatoes, Brazilian orange juice

and U.S. wheat. U.S.-grown foods were just as likely to contain harmful pesticide residues as foods from

other countries. In fact, 11 of the 12 highest residue scores were found on U.S. grown foods, according to

the study. An apple grown in the United States was found to typically contain residues of four pesticides,

and one sample of spinach was found to have residues of 14 different pesticides. In general though, the

analysts noted that just a handful of chemicals accounted for most of the toxicity loading in crops.

According to EFSA a total, more than 67,000 samples of nearly 300 different types of food were analysed

for pesticide residues by national competent authorities. 97.4% of the samples complied with the legal

maximum residue levels (MRLs) of pesticides. .It was concluded that the long-term exposure of

consumers did not raise health concerns. The short-term exposure assessment revealed that for 77 food

samples analysed the acute reference dose (ARfD) might have been exceeded if the pertinent food was

consumed in high amounts.(EFSA,2011)

Monitoring of vegetables and fruits from various sources in Thailand to determine pesticide residues

showed that about 37 percent of 10 types of vegetables (365 samples) were contaminated with

organophosphorus insecticide residues. Residue of 20, 12, 7, 6, 6, 5, 5, 4, 3, and 2 insecticides were

found in kale, cabbage, cowpeas, cauliflower, brassica, cucumber, impomoea, baby corn, tomato and

mushroom subsequently. Most of the residue levels were within the range of Codex maximum residue

level (MRL), About 19.7 percent, 10 percent, 6 percent and 2 percent of analysed samples of kale,

cowpea, impomoea and mushroom subsequently having residues exceed Codex MRL. About 73 percent

of tangerine samples (70) were contaminated with pesticide residues, which were dimethoate, malathion,

monocrotophos and methyl parathion. Monocrotophos was found in about 16 percent of total samples

and about 10 percent of samples having residues exceed Codex MRL (0.2 ppm). For grape, 139

samples from 156 samples were found pesticide residues, i.e. captan, dimethoate, methomyl and

monocrotophos. Monocrotophos was detected in 75 percent of analysed samples and 26 percent of

samples having residue level above Codex MRL( Technical Conference of Agricultural Toxic Substances

Division, Chonburi (Thailand), 23-25 Aug 1995)

.4. MATERIALS AND METHODS

4.1. Sampling methodology

All the fruits and vegetable samples were collected randomly from the markets. All 16 samples were

extracted and analyzed for the 14 organochlorines and 4 synthetic pyrethroides by GC ECD and for 11

organophosphorus pesticides and 2 carbamates by GC NPD.

4.2. Equipments

Gas Chromatographs used for pesticide residue analysis were Finnigan Polaris Qion trap GC/MSn),

Thermoquest-Trace GC with 63

Ni selective Electron-Capture Detector with advanced software

(Chromcard-32 bit Ver 1.06 October 98) and Nucon –GC- 5765 series equipped with Nitrogen

Phosphorus Detector. GC columns employed were capillary column, DB DB- 5 - 5% diphenyl, 95%

dimethyl polysiloxane(30m x 0.25mm x 0.25 m) J & W. Heating mantles, Soxhlet assembly, Rotatory

evaporator (Buchi type) and a 10-l syringe from Hamilton Co. were employed.

4.3. Solvents and Glassware

All the solvents acetone, diethyl ether, hexane (HPLC) grade used for the analysis were purchased from

E-Merck, India. Organic solvents were glass distilled and checked for any pesticide contamination. All

glassware, soxhlet extraction assembly, conical flask, round bottomed flask, glass column, pipettes,

funnel etc were washed with detergent, rinsed with water, dipped in chromic acid for 24 hr and finally

rinsed with distilled water and then hexane.

4.4. Chemicals

Pesticide reference standards of organochlorine pesticides (14) - and HCH, heptachlor, aldrin,

dieldrin, endosulfan and endosulfan sulfate, , pp’-DDD, pp’-DDE, pp-’DDT, endrin synthetic

pyrethroides – cypermethrin, deltamethrin, fenvalerate and g cyhalothrin and organophosphorus

pesticides(11) - dichlorvos, acephate, monocrotofos, dimethoate, chlorpyrifos, malathion,chlorpyrifos

methy, primifos methylquinalfos and ethion and carbamates (2) -carbaryl and carbofuran were obtained

from Sigma chemicals. Other chemicals were purchased from s. d. Fine Chem Ltd.

4.5.Sample extraction and clean up

The samples were analysed for organochlorines by using EPA method 8081 A for organochlorines by

Gas chromatography and EPA Method 8141A for organophosphorus compounds by gas

chromatography -capillary column technique.

Fruits and vegetables

Sample extraction - 50 gm samples were extracted in a blender with 200 ml solvent mixture (n-

hexane:acetone (1+1)) and 25 gm sodium sulphate at high speed for 1.5 min. filtered and reextracted

twice with additional 70 ml aliquot of solvent mixture. The extracted was transferred to 1000 ml separating

funnel , 200 ml of 2% sodium sulphate was added to the separating funnel and shaken vigorously for 2

min. The phases were allowed to separate and the supernatant layer of n- hexane was transferred to 250

ml round bottom flask. Dry extract was collected in a conical flask column washed with 50 ml n- hexane.

The combined extract was concentrated on a rotary vaccum evaporator.

Clean Up

For column clean up 5 ml hexane extract was transferred on to a 400 mm x 25 mm id glass column

containing 10 gm florosil, 8 gm silica gel, 0.3 gm activated charcoal and 2 cm layer of anhydrous sodium

sulphate that had been slurry packed with n- hexane. The solution was allowed to pass through the

column until the liquid level reached the top of the column and vaccum evaporator. The residues were

dissolved in 5 ml HPLC grade n- hexane. From the dissolved residues, eluted with 200 ml of 9

:1 hexane: acetone, concentrated to dryness under reduced pressure at 400C on a rotary evaporator.

Juices

Extraction Methodology: Juice sample were shaken well and filtered through Whatman filter paper

no.1.pH of the samples were checked and it was found to be acidic, pH of all the samples was

neutralised by using 0.1 N NaOH. After filtration, 50 ml of sample was taken in a 1 L capacity separatory

funnel and diluted with 50ml of water and 20 ml of saturated sodium chloride solution was added. The

water sample was partitioned with 100 ml of methylene chloride (thrice) by shaking the separatory funnel

vigorously for 2-3 min releasing the pressure intermittently. The layers were allowed to separate. The

three extracts of methylene chloride layers were combined and passed through anhydrous sodium sulfate

and concentrated to about 1-2 ml using rotary vacuum evaporator. Again 10 ml methylene chloride was

added for adsorption chromatography

Clean up: Clean up was done by EPA Method 3620B- Florosil clean up by column chromatography.

Florisil was activated at 1300 C overnight and cooled in a dessicator before use. Weight of florosil taken

was predetermined by calibration using lauric acid. 20g florosil was packed in a 30cm length and 12 mm

ID glass chromatographic column and anhydrous sodium sulfate was added to the top of the florosil

column (1-2 cm) . The column was pre-eluted with hexane and discarded. Transferred the extract to the

column and eluted with 6% diethyl ether in hexane (200ml), 15% diethyl ether in hexane (200ml), 50%

diethyl ether in hexane(200ml) and finally with diethyl ether (200ml). Eluent was collected and

evaporated to dryness. Final samples were prepared in 2ml hexane (HPLC grade) and analyzed by GC-

ECD for organochlorines and GC equipped with NPD for organophosphorus pesticides.

4.6. Sample Analysis

Calibration of GC system

GC system was calibrated using external standard technique.

Stock standard solution (1000mg/L): Individual stock solutions were prepared by weighing appropriate

amounts of active ingredients in a brown bottle with a Teflon-lined screw cap and dissolving the weighed

standard in HPLC grade hexane. The resulting concentration was corrected for the stated purity if purity

was less than 96%. Stock standard solution was used to prepare primary dilution standards.

Composite stock standard solution- Appropriate volume of each individual stock solution was taken in a

volumetric flask and mixed to obtain composite stock standard solution.

Calibration standard- was prepared at different concentrations by dilution of the composite stock

standard solution with hexane, corresponding to the expected range of concentrations found in samples

and it was used to calibrate (retention time, area count) the instrument response with respect to analyte

concentration.

For Organochlorine and Synthetic Pyrethroides pesticides

Organochlorines and Synthertic Pyrethroides were analysed by Gas Chromatograph (Thermoquest-

Trace GC) with the 63

Ni selective electron-capture detector. The capillary column used was DB- 1701

with carrier and makeup gas as nitrogen with a 1 ml/min and 540 ml/min-flow rate respectively

employing the split less mode. 1.0l of the final extract (2ml) was injected at a temperature of 2500 C.

The oven temperature was kept at 1200C with a hold time of 1 minute, then from 120

0C to 205

0 C at a

rate of 250 C/minute with a hold time of 1 minute , then from 200 to 250

0C at a rate of 2

0 C / minute with

a hold time of 1min and finally from 250 0 C to 290

0 C at 5

0 /minute with a hold time of 5 minute. The

total run length was 45.90minutes. The detector was maintained at 3000C. Peak identification was

performed by the GC software (Chromcard-32 bit Ver 1.06 October 98) calibration table set up with a

relative retention time window of 0.65%.

For Organophosphorus and Carbamate pesticides

Organophosphorus and Carbamates pesticides were analysed by Gas Chromatograph (Thermoquest-

Trace GC). The capillary column used was DB- 5 . The carrier gas and the makeup gas was nitrogen

with a 1.0 ml/min and 15-ml/min-flow rate respectively, hydrogen at 2.3 ml/min and air at 60 ml/min

respectively employing the split less mode. 2.0l of the final extract was injected at a temperature of

2700 C. The oven temperature was kept at 120

0C with a hold time of 1 minute, then from 120

0C to 205

0

C at a rate of 50 C/minute with a hold time of 1 minute then from 205 to 225

0C at a rate of 2

0 C / minute

with a hold time of 1 min and finally from 225 0 C to 260

0 C at 5

0 /minute with a hold time of 5 minute

The total run length was 34.50 minutes. The detector was maintained at 300 0C and Source Current at

2.800 A.

Linearity checks

Gas chromatograph equipped with ECD and NPD were checked for linearity. Instrumental limit of

detection for GC- ECD was 0.01 ng/ml for organochlorines and 0.1 ng/ml for organophosphorus

pesticides.

Laboratory Reagent Blank

An aliquot of reagent grade water was treated exactly as a sample including exposure to all glassware,

equipments, solvents, and reagents used with the sample matrix. No analyte peak was detected in

laboratory reagent blank.

Laboratory fortified blank

An aliquot of reagent grade water to which known amount of pesticides were added in the laboratory in

ppb range was analysed exactly like the sample. The recovery of the pesticides over the background

values obtained from unfortified samples was more than 80 per cent for all the pesticides.

Laboratory fortified sample matrix

An aliquot of sample matrix was prepared to which known quantities of the pesticides were added in the

laboratory in ppb range. This laboratory fortified matrix was analyzed exactly like the sample.15-25% of

the samples (minimum) were fortified with a known concentration of pesticides and percent recovery was

calculated. Extraction and clean up was done as mentioned and the recovery of the pesticides over the

background values obtained from unfortified samples were more than 80 per cent. Standard deviation

and coefficient of variation were less than 10 indicating repeatability of the method. All calculations were

done as described in US EPA method and the amount of residues in samples was obtained in mg/kg

(ppm) of infant food.

4.7 Confirmation

GC-MS

The presence of pesticide residues detected in the samples by GC-ECD and GC-NPD were confirmed

by GC-MS, Model Finnigan Polaris Q Ion trap GC/MSn with EI ionization (70eV), in SIM mode. The

sample and standards were injected using a programmable temperature injector (PTV) with a cold

The capillary column used was DB- 5MS with carrier and makeup gas

as nitrogen with a 1 ml/min and 50 ml/min-flow rate respectively employing the split less mode. 1.0l of

the final extract (2ml) was injected at a temperature of 2500 C. The oven temperature was kept at 120

0C

with a hold time of 1 minute, then from 1200C to 205

0 C at a rate of 25

0 C/minute with a hold time of 1

minute , then from 200 to 2500C at a rate of 2

0 C / minute with a hold time of 1min and finally from 250

0

C to 290 0 C at 5

0 /minute with a hold time of 5 minute keeping the Ion source at 275

0C; Multiplier:1100

Volts; AGC:50 , 3 microscan; Default : Tune parameters: Autotune Tune File. Full Scan :50 650 m/z,

SIM: Exact Mass +/- 0.1 amu.

6. Results and Discussion

A total of 16 samples of apple, grapes, plums , peaches, orange, from different countries- USa Australia

New Zealand Thailand, Italy, France and Turkey ere analysed fo Organochlorine(14),

Organophosphorus(11), Synthetic pyrethroides(4) and Carbamates(2).

The pesticides found in fruits and vegetables mainly included lindane , DDE, endosulfan, deltamethrin,

gamma cyhalothrin, dimethoate, malathion, chlorpyriphos, monocrotophos, quinalfos primifos

methyland cypermethrin. The banned organochlorine pesticides detected in imported fruits and

vegetables were DDE, lindane and endosulfan. DDT, which is still used in the malaria eradication

programme, find their illegal way into the agriculture system, while the residue of other banned pesticides

can be found due to their presence in the soil and water.

Lindane was detected in 56 % of the samples (9/16) at an average concentration of 0.48ppb which is

within the MRL in the country of origin and and also within MRL prescribed by Food safety and standards

Authority of India (FSSAI) and CODEX.

DDE an organochlorine pesticide , metabolite of DDT was detected 31% of the samples(5/16) at an

average concentration of 0.26 ppb which is within the MRL prescribed by FSSAI and Codex.

Endosulfan was detected in 19% of the samples(3/19) at an average concentration of 1.03 ppb in the

range of 1.39-9.05 ppb.

Deltamethrin , synthetic pyrethroid insecticide was detected in only one sample i.e plums from USA at

an average concentration of 1.05ppb which is well within the MRL presrcibed by Codex for fruits and

vegetables

Chlorpyrifos is a moderately persistent insecticide effective against mosquito and fly larvae, cabbage

root fly, aphids. Chloropyrifos has become one of the most widely applied insecticides in homes

restaurants against cockroaches, termites. Chlorpyrifos was detected in 31% of the samples(5/16)

analysed. The range of concentration in the 16 samples varied from 27.53-857.19. Average

concentration of 86.26 ppb of chlorpyrifos was detected in all the samples that is within the MRL

prescribed by FSSAI(500ppb) and Codex (1000ppb) for chlorpyrifos for fruits and vegetables.

Chlorpyrifos in Grapes (red) from USA was detected at an average concentration of 103.492 ppb

which is 10 times the limit of 10 ppb precribed by EPA for chlorpyrifos in apples.

In another sample of Grapes (black) from Thailand chlorpyrifos was detected at an average

concentration of 857.19ppb which is almost twice the limit available for Chlorpyrifos in grapes in

Thailand .

Malathion was present in 31% of the 16 samples (5/16) analysedat a an average concentration of of

48.97ppb in the range of 3.37-404.74ppb which is within the MRL provided by CODEX for Malathion in

Fruits abnd Vegetables.

Dimethoate was detected in 2 samples out of 16 samples analysed at an average concentration of

3.63ppb ranging from 6.53 to 51.57 ppb .

Monocrotofos was detected in 3 out of the 16 samples analyzed at an average concentration of 60.55 ppb

ranging from 19.74-819.21ppb. Highest concentration of monocrotofos was detected in Plum from

Australia .There is no MRL for monocrotofos in fruits and vegetables.

Quinalfos was detected in 25 percent of the samples at an average concentration of 8.68ppb.

Primifos –methyl was detected in only 3 sample at an average concentration of 1.68 ppb in the range of

9.71-16.11ppb.

Ethion was detected in 2 out of 13 samples at an average concentration of 7.6975 ppb.

Carbaryl was detected in 5 samples out of 16 samples at an average concentration of 86.77ppb in the

range of 45.16-950.64ppb which is within the MRL given by CODEX(5000ppb) for fruits nd Vegetables.

Carbofuran was detected in only 2 out 16 samples . at an average concentration of 22.1059ppb . Highest

concentration was detected in Peaches imported from Australia.

7. CONCLUSIONS

31 pesticides belonging to 4 different classes -Organochlorines (14), Synthetic pyrethroides (4)

Organophosphorus (11) and Carbamates (2) pesticides were analysed in 16 imported fruit and

vegetable samples. Multiple residues (i.e. single samples which contain residues of more than one

pesticide were detected in imported fruits and vegetables samples available in the Delhi market. The

highest concentration of total pesticides was detected in grapes from thailand i.e 2230.61 ppb (2.23ppm)

, followed by plums from Australia (1424.29 ppb)and then peaches from Australia(794.16ppb). Among

the different classes of pesticides detected highest residues were detected of Organophosphorus

pesticides (217.46ppb) followed by Carbamates (108.88ppb), then Organochlorine (4.026ppb) and finally

the synthetic pyrethroides (0.1496ppb). 87.5% of the imported fruits and vegetables were

compliant with the national and international regulations only 12.5% of the

samples that is 2 grape samples (one from US and one from Thailand) violated

the national regulations for chlorpyrifos but were within the MRL set by CODEX.

Out of the 31 pesticides analysed only Chlorpyrifos was found to be above MRL set for the pesticide in

the country from where imported. Other pesticides detected were compliant with national and

international regulations governing the presence of pesticide residues in agricultural produce. Multiple

residues in one sample can result from the application of different types of pesticides to protect the crop

against different pests, diseases or other threats having an impact on the quality or yield of crops, from

mixing of lots with different treatments, contaminations, but also from practices which do not respect the

principles of good plant protection practice. It should be noted that the presence of pesticides, even an

exceedance of an MRL, does not imply that this is a food safety concern. To ascertain the latter

exposure assessments are required.

8. References

[1] Maria, H. W. M.C.; Regina, T. M. C.; Jaı´za, L. M.; Shirley ; Ka´tia M. P. M. Extractionand Clean-Up

Method for the Determination of Twenty Organochlorine PesticideResidues in Tomatoes by GLC-ECD. J.

High. Resol. Chromatogr.1999, 22, 619–622.

[2] Jos´e, L. T; Consuelo, S´.B; Beatriz, A.; Lorena G.Analysis of pesticide Residues in Juice and

beverage, Crit. Rev. in anal. chem. 2004, 34.

[3] Flemming, H. F. Analysis of Residues of Seven Pesticides in Some Fruits andVegetables by Means of

High Pressure Liquid Chromatography. J. F. Bergm.Vertag.1981, 173, 95-98.

[4] Krbic, B. S. Organochlorine and organophosphate pesticide residues in wheat varietiesfrom Serbia. F.

Addi. and Contam. 2007,24: 695–703.

[5] Carl, F. Varian Chromatography Systems. GC/MS/MS Analysis for PesticideResidues in Agricultural

Products. GC-MS 40,0595.

[6] WHO Regional Office for Africa. International, Regional, Subregional and NationalCooperation in Food

Safety in Africa. FAO/WHO Regional Conference on Food Safetyfor Africa. Harare, Zimbabwe.2005.

Table 1 Organochlorines in imported fruits and vegetables in Fruits and vegetables

Organochlorines

S.No Code No.

Food Item Country a-HCH b-HCH

g-HCH d-HCH t-HCH DDE

DDD DDT t-DDT a-

endo b-

endo Endosulfan sulfate

t-endo Total Ocs

1 001 Grapes Red USA 0.00 0.49 0.00 0.00 0.49 0.30 0.00 0(50) 0.30 0.00 0.00 0.00 0.00 0.79

2 011 Plum USA 0.00 0.00 0.34 0.00 0.34 2.19 0.00 0(200) 2.19 0.00 9.05 0(2000) 9.05 11.59

3 012 Pear USA 0.00 0.00

0.8106(NA)

0.11 0.11 0.35 0.00 0(100) 0.35 0.00 0.00 0(2000) 0.00

1.28

4 005 Peach Australia 0.00 3.05

0.723(2000)

0.00 3.05 0.00 0.00 0(1000) 0.00 0.00 0.00 0.00 0.00

3.77

5 006 Plum Australia 0.00 0.07 0(500) 0.00 0.07 0.00 0.00 0(1000) 0.00 0.00 0.00 0.00 0.00 0.07

6 008 Mandarin Australia 0.00 0.00

0.1053(500)

0.00 0.00 0.00 0.00 0(1000) 0.00 0.00 0.00 0.00 0.00

0.11

7 010 Apple

New Zea Land

0.00 0.00 2.40 1.22 3.62 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

3.62

8 002 Grapes Black Thailand 0.00 1.28 0.64 0.00 1.93 0.00 0.00 0(100) 0.00 0.00 0.00 0.00

0.00 1.93

9 007 Mini Orange Thailand 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

10 013 Guava Thailand 0.00 0.00 0.89 1.34 2.22 0.92 0.71 0.00 1.62 0.00 0.00 0.00 0.00 3.84

11 014 Dragon Fruit Thailand 0.00 0.00 1.05 0.99 2.04 0.44 0.00 0.00 0.44 0.99 0.39 0.00 1.39 3.87

12 015 Snow peas Thailand 0.00 0.00 0.00 0.69 0.69 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.69

13 016 Asparagus Thailand 0.00 0.31 0.00 0.29 0.60 0.00 0.00 6.28(100) 0.00 0.00 0.00 0.00 0.00 6.88

14 009 Kiwi Italy 0.00

19.88

and 0.00 19.88 0.00 0.00 0.00 0.00 0.00 5.96 0.00 5.96

26.56

15 003 Apple France 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

16 004 Apricot Turkey 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Juices

17 017 Real Mixed Fruit India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

18 018 Real Grape India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

19 019 Real Orange India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

20 020

Tropicana Mixed Fruit

India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.00

21 021

Tropicana Grapes

India 0.00 0.00 0.00

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.00

22 022 Onjus Grapes India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

MEAN 0.00 1.57 0.48 0.29 2.34 0.26 0.04 0.39 0.70 0.06 0.96 0.00 1.02 4.06

Table 2 Synthetic pyrethroides ,organophosphorus and carbamates in imported fruits and vegetables

Synthetic Pyrethroides

Organophosphorus

Carbamates

S.No

Code No.

Food Item Country Deltamethrin

g- cyhalothri

n

Total SP

Dimethoate

Monocrotofos

Malathion Chlorpyrifos Quinalfo

s Ethion

Primifos -

methyl

Total OP Carbaryl Carbofuran

Total NMC Total

Pesticides

1 001 Grapes Red USA 0.00 0.00 0.00

0 (2000)

0.00 99.33

(12000) 103.492

(10) 0.00 0.00 0.00 202.82

168.20 (10000)

0.00 168.20 371.81

2 011 Plum USA 1.05 1.33 2.39 0.00 0.00 0(8000) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

13.98

3 012 Pear USA

0 (200)

0 (300)

0.00 0.00 0.00 0(8000) 0

(50) 24.88 0.00 0.00 24.88 0(12000) 0.00 0.00

26.16

4 005 Peach Australia 0.00 0.00 0.00

51.57 (3000)

0.00 101.17 76.81 (1000)

0.00 112.65 0.00 290.62 96.331 (10000)

351.86 448.19 794.16

5 006 Plum Australia 0.00 0.00 0.00 0.00 819.22 161.84 315.10 0.00 0.00 0.00 1296.15 128.06 0.00 128.06 1424.29

6 008 Mandarin Australia 0.00 0.00 0.00 0.00 0.00 0.00 0.00 72.55 0.00 0.00 72.55 0.00 0.00 0.00 72.66

7 010 Apple

New Zea Land

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.62

8 002

Grapes Black

Thailand 0.00 0.00 0.00 0.00 0.00 404.74 (5000)

857.19 (500)

0.00 0.00 16.11 1278.04 950.64 (5000)

0.00 950.64 2230.61

9 007 Mini Orange Thailand 0.00 0.00 0.00

6.53 (5000)

129.87 3.372 (7000)

27.53 (1000)

0.00 0.00 0.00 160.77 0

(15000) 0.00 0.00

167.30

10 013 Guava Thailand 0.00 0.00 0.00 0.00 0.00 0.00 0.00 35.62 10.51 0.00 46.13 0.00 0.00 0.00 49.97

11 014 Dragon Fruit Thailand 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.87

12 015 Snow peas Thailand 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.90

13

016 Asparagus Thailand 0.00 0.00 0.00 0(50) 0.00 0

(1000) 0.00 0.00 0.00 9.71 9.71

0 (15000)

0.00 0.00

16.59

14 009 Kiwi Italy 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.77 0.00 0.00 5.77 0.00 0.00 0.00 32.33

15 003 Apple France

0 (200)

0.00 0.00 0.00 0.00 13.0665

(20) 0

(500) 0.00 0.00 1.09 14.15

45.16 (50)

0.00 45.16 59.31

16 004 Apricot Turkey 0.00 0.00 0.00 0.00 19.74 0.00 0.00 0.00 0.00 0.00 19.74 0.00 1.83 1.83 21.57

Juices 0.00 0.00 0.00

17 017

Real Mixed Fruit

India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 192.86

18 018 Real Grape India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 24.37 0.00 0.00 24.37 0.00 0.00 0.00 24.37

19 019 Real Orange India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.73 0.00 1.73 0.00 0.00 0.00 1.73

20 020 Tropicana India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Mixed Fruit

21 021

Tropicana Grapes

India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

22 022

Onjus Grapes

India 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

MEAN 0.07 0.08 0.15 3.63 60.55 48.97 86.26 8.68 7.70 1.68 217.54 86.77 22.11 108.88 330.63

1. United States- EPA 40CFR180 (e-CFR) to 4 Oct 2010. Updated 4 October 2010 2. Australia -FSANZ Joint Food Standards Code 1.4.2 to v122 (5 May 2011) and APVMA Var 3 (23 Sep 2011). NZ MRLs also recognised. Includes Proposed MRLs ( APVMA var to -

11 Oct 2011. Updated Oct2011

3. European Union Regulation 396/2005 Annexes amended to 3 Oct 2011 (Reg978/2011). Proposed MRLs to SANCO 12225 (Oct 2011). Default MRL is 0.01ppm. Updated Oct 2011

Table 3. Pesticide residues detected in Imported fruits and vegetables

S.No. Pesticide

No of Samples

No of samples in which residues detected

Percentage in which residues detected (%) Mean Range(ppb)

MRL -1 FSSAI (ppb)

MRL - 2 Codex (ppb)

1 Lindane 16 9 56 0.48 0.11-2.40 100 500

2 DDE 16 5 31 0.26 0.30-2.19 3500

3 Endosulfan 16 3 19 1.03 1.39-9.05

4 deltamethrin 16 1 6 0.07 0-1.05 50

5 Gamma cyhalothrin 16 1 6 0.08 0-1.34

6 Dimethoate 16 2 13 3.63 6.53-51.57 2000 1000

7 Monocrotofos 16 3 19 60.55 19.74-819.21

8 Malathion 16 6 38 48.97 3.37-404.74 8000

9 Chlorpyrifos 16 5 31 86.26 27.53-857.19 500 1000

10 Quinalfos 16 4 25 8.68 5.77-72.55

11 Primifos -methyl 16 3 19 1.68 9.71-16.11

12 Ethion 16 2 13 7.70 10.51-112.65

13 Carbaryl 16 5 31 86.77 45.16-950.64 5000

14 carbofuran 16 2 13 22.11 1.83-351.86

1. FSSAI Food Safety and Standards Regulations 2010 (2-15015/30/2010-FSSAI October 2010) - Part 8.3. PFA (2nd Amendm) GSR 264 of 30 Mar 2011. Updated July 2011

2.Codex Codex Alimentarius to CAC34 July 2011 (CCPR REP11/PR). Updated Aug 2011