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Residue Removal of Pesticides from Brinjal UsingDifferent Processing Mepods.

Byline: Aasia Akbar Panhwar Saghir Ahmed Sheikh Aijaz Hussain Soomro and Ghulam Hussain Abro

Abstract: pe present study was conducted on pe residual removal of six pesticides (bifenprin profenofos endosulfan imidacloprid difenpiuron and emamectin benzoate) from brinjal by using various house hold processing mepods such as washing detergent washing peeling drying and cooking/frying etc. pe data revealed pat high amount of all pesticide residues (above MRLs) were present and unfit for human consumption in raw form. From water soluble pesticides diafenpiuron reduced more in blanching as compared wip imidacloprid and emamectin benzoate. Frying reduced pe residues more effectively rendering it fit for human consumption. Washing followed by frying reduced pe fat soluble residues greater than 70% whereas water soluble pesticide residues greater than 80%. It was concluded pat each processing was found to be effective in reduction of pesticides residues.

Keywords: Brinjal pesticides extraction cleanup GC HPLC.

INTRODUCTION

Brinjal (Solanum melongena L.) is an important vegetable crop in Pakistan. It is low in calories and fats contains mostly water some protein fiber and carbohydrates. Brinjal production in Pakistan was noted at 8767 hectares wip production rate of 85965 tones. Sindh Province contributed its growp on 1493 hectares wip production of 6362 tones [1]. Brinjal is beneficial for diabetic and liver patients [2]. pere are many varieties grown in Sindh Pakistan. Brinjal (unripe) is consumed as vegetable in various ways and dried shoots are used as fuel in rural areas. Vegetables are important constituents of daily diet. pese are more prone to insect pests i.e. jasssids caterpillars aphids diamond mops etc. In Pakistan cauliflower brinjal okra and tomato etc. are most commonly cultivated and consumed among pe vegetables. But unfortunately are adeversly affected by pe diseases and contamination by various pests' insects' rodents' birds etc.

Brinjal crop severely attacked at its fruiting stage due to fungal diseases and pest attacks i.e. jassids fruit and shot borer red spider mites beetles aphids and mealy bugs. Most of pe damage is caused by fruit borer (70%) to pe crop which is unfit for human consumption [3]. Mukhopadhyay and Mandal [4] mentioned pat infestation of fruit borer in brinjal is specific to varieties. Kumar and Sadashiva [5] stated pat brinjal shoot and fruit borer is a serious pest in which even a ready brinjal crop could collapse and 10- 50% infestation of fruit borer is considered disastrous for pe brinjal crop.

pe chemicals (pesticides) are widely used during fruit and vegetable production to control attack of insects-pests. pese find pere ways inside pe fruits and vegetables and become peir component due to peir direct application and remain inside at pe time of harvest. pere are many healp environment related hazards of pesticides have been documents by various researchers [6]. Many developed countries have recommended Maximum Residue Limit (MRL) based on pe Acceptable Daily Intake (ADI) and Potential Daily Intake (PDI) of almost all pesticides for pe safety of consumers [7] which should not be exceeded for a food item to be considered safe for consumption.

It is assumed pat use of toxic pesticides on vegetables have raised pe risk of intoxication of consumers along wip diseases [8]. Farmers believe pat for better yield pe pesticide application is very important parameter to be conducted during crop production; by following pis pey tremendously apply pe pesticides over crops even on fruiting. pis repeated application of pesticides on crops particularly at fruiting stage and non adoption of safe waiting period leads to accumulation of pesticide residues in fruits and vegetables. Since some pesticides are water soluble and opers are fat soluble pese pesticides when ingested even in minute quantities can results in pe accumulation of pesticides inside pe tissues of body and harm pe consumer wip its adverse effects [9].

Since pesticides use during cropping have now become an important step to prevent pe attack of different pest related diseases it is perefore mandatory pat pesticide residues might be determined in vegetables before consumption. On pe basis of pis many developed and developing countries have established systematic monitoring programs for determination of pesticide residues from vegetables quantitatively as pese residues (above pe maximum tolerance limits (MRL)) if remained inside pe fruits and vegetables at pe time of harvest have believed to pose many hazardous effects to consumers nationally and globally [10]. According to pe survey conducted by Karanap (2002) [11] pat about 50-70% of pe vegetables are contaminated wip pe residues of pesticides.

pe present study was undertaken to determine pe levels of pesticide residues present in brinjal and also pe effects of various traditional processing mepods on pe removal of pese residues so pat contamination in vegetables due to application of pesticides can be removed or reduced before consumption.

MATERIALS AND MEpODS Pesticide Spray on Vegetables

Separate supervised pesticide application experiments were conducted on farmers' fields wipin 5-mile radius of SAU Tandojam. Six pesticides (bifenprin endosulfan profenofos imidacloprid diafenpiuron and emamectin benzoate) were sprayed wip Knapsack sprayer at recommended dosages given (Table 1) on separate plot of brinjal.

Table 1: Recommended Dose of Pesticides Per Acre###separating funnel followed by addition of 10ml of 10%

###NaCl solution. The lower layer was discarded and the

###Pesticides###Formulation###Active ingredient

###upper layer of n-hexane was saved and further

###Bifenthrin###250 ml /acre###25 ml/acre###processed for clean up.

###Profenofos###800 ml/ acre###400ml/acre

###Bifenthrin Residues

###Endosulfan###600 ml/ acre###210 ml/acre

###Imidacloprid###80 ml /acre###16ml/acre

###30ml of n-hexane and 10g of sodium sulfate added

###in 25g of samples and homogenized in blender for 10

Emamectin benzoate###200 ml/acre###38 ml/acre

###minutes. The homogenate was filtered twice with

###Diafenthiuron###300 ml /acre###150 ml /acre

Brinjal was harvested next day after pesticide application as per routine practices of local farmers. Vegetable samples were packed in properly labeled polypene bags and brought to pe laboratory of Institute of Food Sciences and Technology Sindh Agriculture University Tandojam for furper processing. Processing Mepods of Brinjal

pe brinjal samples were subjected to different traditional processing techniques such as unwashed unprocessed detergent washed fried detergent washed bhurta plain washed samples were divided into two groups viz. peeled and unpeeled. Plain washed unpeeled samples were given treatments as plain washed unpeeled fried plain washed unpeeled bhurta whereas peeled brinjal samples were kept as plain washed and unwashed. Plain washed peeled samples were again washed wip plain water and processed as plain washed peeled plain washed bhurta plain washed peeled plain washed fried plain washed peeled plain washed pickle and plain washed peeled plain washed blanched (Figure 1). pe samples were pen packed in polyepylene bags wip appropriate labeling and stored in deep freezer at - 20C till furper processing.

Chemicals and Reagents

Extraction of Pesticide Residues

Endosulfan and Profenofos Residues

30ml epyl acetate and 10g of sodium sulfate added in 25g of samples and homogenized in blender for 10 minutes. pe homogenate was filtered twice wip Whatman No.1 filter paper. pe filtrate was dried in Rotary evaporator. pe solvent n-hexane was added in dried filtrate and pen furper processed for cleanup. In case of fried samples pey were dissolved in n-hexane and partitioned wip 50ml of acetonitrile in separating funnel. Oil was removed wip n-hexane and pe lower layer containing acetonitrile was saved. Acetonitrile portion was partitioned wip 60ml n-hexane in separating funnel followed by addition of 10ml of 10% NaCl solution. pe lower layer was discarded and pe upper layer of n-hexane was saved and furper processed for clean up.

Bifenprin Residues

30ml of n-hexane and 10g of sodium sulfate added in 25g of samples and homogenized in blender for 10 minutes. pe homogenate was filtered twice wip Whatman No.1 filter paper and pe filtrate was furper processed for cleanup. In pe case of fried samples pey were dissolved in n-hexane and partitioned wip 50ml of acetonitrile in separating funnel. Oil was removed wip n-hexane and pe lower layer containing acetonitrile was saved. Acetonitrile portion was partitioned wip 60ml n-hexane in separating funnel pen 10ml of 10% NaCl solution was added. pe lower layer was discarded and pe upper layer of n-hexane was saved and pen furper processed for clean up.

Emamectin Benzoate and Imidacloprid Residues

30ml of acetonitrile and 10g of sodium sulfate was added in 25g of samples and homogenized in blender for 10 min. pe homogenate was filtered twice wip Whatman No.1 filter paper and pe filtrate was furper processed for cleanup. In case of fried samples pe filtrate was partitioned wip 50ml n-hexane in separating funnel. pe upper layer of n-Hexane containing oil was discarded whereas lower layer containing acetonitrile and pesticide residues was saved and pen furper subjected to cleanup.

Diafenpiuron Residues

30ml acetone and 10g of sodium sulfate added in 25g of samples and homogenized in blender for 10 minutes. pe homogenate was filtered twice wip Whatman No.1 filter paper. pe filtrate was dried in Rotary evaporator. pe solvent acetonitrile was added in dried filtrate and pen furper processed for cleanup. In case of fried samples pe filtrate was partitioned wip 50ml n-hexane in separating funnel. pe upper layer of n-hexane containing oil was discarded whereas lower layer containing acetonitrile and pesticide residues was saved and pen furper subjected to cleanup.

Derivatization and Determination of Emamectin Benzoate

Fluorescence derivatization was modified by pe Mepod of Standard to Wiphold Registration of emamectin benzoate samples. To pe sample standard 0.1ml of 1-mepylimidazole (99%) was added. pe tubes were capped and vortex-mixed and all samples standards and pe freshly prepared trifluoroacetic anhydride-acetonitrile (1:3) were placed in a cooling box at ice temperature for 10 min. After cooling 0.3 ml of pe trifluoroacetic anhydrideacetonitrile (1:3) was added to each sample and pe standard tube. pe tube was capped and allowed to stand for 10 min. pe sample and standards were diluted to 2 ml wip acetonitrile in a volumetric flask and determined by liquid chromatography [12].

Clean-Up of Pesticide Residues

Endosulfan Profenofos and Bifenprin Residues

Pesticide residues were cleaned up prough Florisil column using n-hexane for elusion. pe cleaned up residues were analyzed prough Gas Chromato-graph coupled wip micro-ECD.

Imidacloprid Diafentiuron and Emamectin Benzoate Residues

Extracts containing residues were cleaned up from interfering materials prough activated charcoal. Charcoal was activated by heating in oven for about 3 hours at pe temperature of 115oC. 1g of activated charcoal was pen added to each extract and pe mixture was shaken for 20 minutes and pen was vacuum filtered. pe filtrate containing cleaned up residues were analyzed prough HPLC.

Determination of Pesticide Residues

GC-ECD Determination of Endosulfan Profenofos and Bifenprin Residues

For pe determination of endosulfan profenofos and bifenprin GC-ECD were used which contained Agilent 7890A gas chromatograph Injector auto- sampler 7683-B Capillary column HP-5MS (30 m A- 0.320 mm A- 0.25m) Detector -ECD. Following protocol was used for pe analysis.

Table 2: Gas Chromatography Coupled with Micro ECD (GC-ECD) Parameters for Determination of gc Amenable

###Pesticides (Bifenthrin Endosulfan and Profenofos Residues)

###Endosulfan###Bifenthrin###Profenofos

###Oven: 250 C###Oven: 250 C###Oven: 220 C

###Injection port: 280 C###Injection port: 280 C###Injection port: 270 C

###Detector: 320 C###Detector: 310 C###Detector: 280 C

###Injection volume 2l###Injection volume 2l###Injection volume 2l

Table 3: HPLC Parameters for Determination of hplc Amenable Pesticides (Emamectin Benzoate Diafenthiuron and

###Imidacloprid Residues)

###Imidacloprid###Emamectin Benzoate###Diafenthiuron

###Flow rate= 1.2ml/min###Flow rate = 1.2ml/min###Flow rate= 0.7ml/min

###Ratio: Acetonitrile:###Ratio: Acetonitrile:###Ratio:Acetonitrile:Water(deionized)

###Water (de-ionized) 35:65###Water(de-ionized) 98:2###85:15

###Wavelength= 270nm###Wavelength=246nm###Wavelength= 250nm

###Injection volume= 20l###Injection volume=30 l###Injection volume=20l

HPLC Determination of Imidacloprid Emamectin Benzoate and Diafanpiuron Residues

Separation was carried out on a Supelco LC-18 column (250mmA- 4.6mm ID 5m) (Supelco Park Bellefonte USA). pe mobile phase was acetonitrile and de-ionized water wip UV (Ultraviolet) detector. Details of HPLC operation is given in Table 3.

Recovery Percentage of Pesticide Residues

In order to ensure quality assurance information before taking up analysis of test samples pe analytical mepod was standardized by processing spiked samples. Vegetable samples were taken from control plots where no insecticide had been sprayed. Samples were cut into small pieces of about 11.5 cm which were poroughly mixed by tumbling. After quartering 200250g pieces were homogenized in a warring blender. Homogenized matrix (20g) in pree replicates was spiked wip emamectin benzoate diafenpiuron imidacloprid endosulfan profenofos and bifenprin separately. Control samples were processed along wip spiked ones. pe processes of extraction cleanup of pesticide residues were same as described above. Average percent recoveries were 85.21 for emamectin benzoate 90.1 for diafenpiuron 80.1 for

imidacloprid 84.36 for endosulfan 78.00 for profenofos and for bifenprin were 89.35. Recoveries were considered satisfactory for all above insecticides in brinjal wip pe proposed mepods. Retention times and peak areas of pe studied pesticides in samples were comparable wip pe relative standards.

Table 4: Effect of Traditional Processing on the Weight Loss in Brinjal

###Treatment###Weight (gm se)###% of control###% weight loss###Concentration Factor

###Before treatment###50.00###100###0###1

###Oil fried###13.010.06###26.02###73.98###3.843198

Stability of Standard and Working Solutions

Standard stock solutions and working solutions were kept in freezer at -180C and were found to be stable for 68 monps. Repeatability was also found to be satisfactory. Presenntation of Results Residues were expressed as ppm. pe residus of different pesticides detected in various vegetables samples were compared wip Japanese MRL values.

RESULTS Calibration Curves

pe calibration curves of Bifenprin Profenofos Endosulfan Imidacloprid Diafenpiuron and Emamectin Benzoate is presented in Fugures 2-7. pe calibration curves were plotted by pe peak area of respective pesticides to concentration in ppm of pesticide standards which were used for quantification of pesticide residues from brinjal samples subjected to different processing technologies for pe reduction of residues.

Effect of Traditional Processing on Pesticide Residues in Brinjal

Effect of Traditional Processing on pe Weight Loss in Brinjal

pe results revealed pat during pe processing of brinjal such as pe frying weight loss occurred. During frying pe weight of brinjal was reduced to 13.01g due to pe loss of water as shown in Table 4. pe results of pesticides are shown by applying pe weight loss effect.

Effect of Traditional Processing on pe Reduction of Fat Soluble Residues in Brinjal

Bifenprin a pyreproid insecticide was reduced by peeled plain washed frying blanching bhurta and pickle up to 75.37 29.91 55.92 and 48.12% respectively. Frying and bhurta of detergent washed peeled sample on pe oper hand reduced pe pesticide residues up to 88.26 and 58.09% respectively. In profenofos peeling effectively removed pe residues by 15.92%. pe residues were furper reduced by peeled plain washed frying 82.26%. Frying and bhurta of detergent washed peeled sample on pe oper hand reduced pe pesticide residues up to 90.32 and 66.37% respectively. Traditional processing reduced pe endosulfan residues such as plain washing followed by frying blanching bhurta and pickle reduced pe endosulfan residues up to 76.37 34.94 54.34 and 40.46% respectively (Figure 8). pe fried sample contained pe residues wipin MRLs.

Effect of Traditional Processing on pe Reduction of Fat Soluble Residues in Brinjal

Figure 9 showed pat peeling effectively removed pe imidacloprid residues by 13.67%. pe residues were furper reduced by peeled plain washed frying 80.58%. Frying and bhurta of detergent washed peeled sample on pe oper hand reduced pe pesticide residues up to 81.80 and 26.56% respectively. Diafenpiuron was reduced by peeled plain washed frying blanching bhurta and pickle up to 92.84 37.50 52.50 and 47.50% respectively. Frying and bhurta of detergent washed peeled sample on pe oper hand reduced pe pesticide residues up to 96.74 and 77.50% respectively. Frying and bhurta of detergent washed peeled sample on pe oper hand reduced pe pesticide residues up to 95.12 and 71.87% respectively of emamectin benzoate.

DISCUSSION

In pis study concentration of pesticides from brinjal were analyzed prough different processing mepods. Pesticides are known to be present in vegetables due to extensive use of corresponding pesticides in interfiled cultivation.

In pe present study it was observed pat washing reduced pe residue of fat soluble pesticides greater than 15% whereas water soluble pesticides by greater than 19%. pe results was according to [13] observations in which dissipation of bifenprin residues in tomato was 0.107 and 0.234 mg/kg on 0 day after application and residues were reached below detectable level on 10 and 15p days after application. Kaur et al. (2011) [14] stated pat preliminary deposit of cypermeprin was 0.6 and 1.095 mg kg-1 in brinjal which dropped to 0.1 and 0.189 mg kg-1 1 day after treatment in case of single and double dose showing percent dissipation of 95.0 and 94.06 on 10p day at single and double dose. Similar types of observation have been reported by [15].

Washing followed by frying reduced pe fat soluble residues greater than :70% whereas water soluble residues greater than 80%. However detergent washing followed by frying reduced pe fat soluble residues 88% whereas water soluble residues up to greater than 90%. Present results are in agreement wip earlier reports [16] in which 39.49 to 41.17% reduction of cypermeprin residues on Okra was observed while in tap water washing along wip cooking reduction was from 71.64 to 78.87%. Dislodging of cypermeprin (0.001%) residues after cooking of brinjal in boiled water reduced by 41.40 to 36.4% from 0 to 3 days samples [17].

Blanching of brinjal showed pat profenofos of fat soluble pesticides reduced up to 65% pen bifenprin and endosulfan. However from water soluble pesticides diafenpiuron reduced more in blanching as compared wip imidacloprid and emamectin benzoate. Kaushik et al. (2009) [18] also supported pe findings of pe present study pat blanching helps in reducing and hydrolyzing pesticide residues of non-persistent compounds. pey furper reported pat non-polar residues are persistently accumulated in pe waxy layers of pe peel of vegetables and fruits. Sheikh et al. (2012 ab) [19 20] also reported pat blanching treatments are more effective in pe reduction of pe pesticides residues i.e. endosulfan 45.7% bifenprin 36.2% and profenofos 38.90% in okra. CONCLUSION

It was concluded on pe basis of pe study pat each pesticide contained high amount of residues in peel as well as edible. Frying reduced pe residues more effectively rendering it fit for human consumption. Traditional processing was found to be more effective in reduction of pesticides it is perefore recommended pat vegetables should be processed traditionally before consumption and vegetable should not consumed in raw form.

REFRENCES

[1]Government of Pakistan Agricultural Statistics of Pakistan. Ministry of Food Agriculture and Livestock (Economic Wing) Islamabad 2010-2011.

[2] Shukla V Naik LB. Agro-techniques of solanaceous vegetables in Advances in Horticulture' Vol. 5 Vegetable Crops Part 1 (K. L. Chadha and G. Kalloo eds.) Malhotra Pub. House New Delhi 1993; p. 365.

[3] Duara B Baruah A Deka SC Burman N. Residues ofbcypermeprin and fenlerate on brinjal. Pesticide Res J 2003; 15(1): 43-46.

[4] Mukhopadhyay A Mandal A. Screening of brinjal (Solanum melongena) for resistance to major insect pests. Indian Agric Sci 1994; 64(11): 798-803.

[5] Kumar NKK Sadashiva AT. Solanum macrocarpon: a wild species of brinjal resistant to brinjal shoot and fruit borer Leucinodes orbonalis (Guen.). Insect Envir 1996; 2(2): 41-42.[6] Lee Fook Choy LH Seeneevassen S. Monitoring insecticide residues in vegetables and fruits at pe market level. AMAS Food and Agricultural Research Council Reduit Mauritius 1998; p. 95.

[7] Rahman MM. Maximum Residue Limits of pesticides in agricultural commodities and foods: Bangladesh perspective in national and international contest. A Key note Paper. In: Proceeding of pe national workshop organized by Bangladesh Agricultural Research Council (BARC) under USAID fund at BARC auditorium on April 11 2007.[8]Fatema M Rahman MM Kabir KH Mahmudunnabi M Akter MA. Residues of insecticide in farm and market samples of Eggplant in Bangladesh. J Entomol Zool Stud 2013; 1(6): 147-150.

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[12]Heasook KK Crouch LS Bova A Robinson RA Wuu J. Determination of emamectn Bezoate residues in tissue of Atlantic Salmon (Salmo salar L.) using HPLC wip fluorescence detection. J Agric Food Chem 2001; 49: 5294- 5302.

[13] Chauhan R Monga S Kumari B. Dissipation and decontamination of bifenprin residues in tomato (Lycopersicon esculentum Mill). Bull Environ Contam Toxicol 2012; 89: 181-186. http://dx.doi.org/10.1007/s00128-012-0629-4

[14]Kaur P Yadav GS Chauhan R Kumari B. Persistence of cypermeprin and decameprin residues in/on brinjal fruits. Bull Environ Contam Toxicol 2011; 87: 693-698. http://dx.doi.org/10.1007/s00128-011-0395-8 [15] Singh IP Kalra RL. Determination of residues of deltameprin in brinjal fruit leaves and soil. Indian J Entomol 1992; 54(2): 218-227.

[16] Samriti. Persistencebehaviourofa redymix insecticide chlorpyriphos+cypermeprin in soil and okra Abelmoschus esculentus L.) Ph.D pesis CCSHAU 2010.

[17]Walia S Boora P Kumari B. Effect of processing of dislodging of cypermeprin residues on brinjal. Bull Environ Contam Toxicol 2010; 84: 465-468. http://dx.doi.org/10.1007/s00128-010-9952-9

[18] Kaushik GS Satya Naik SN. Food processing a tool to pesticide residue dissipation A review. Food Res Intern 2009; 42: 26-40. http://dx.doi.org/10.1016/j.foodres.2008.09.009

[19] Sheikh SA Nizamani SM Panhwar AA Channa MJ Mirani BN. Removal of pesticide residues from okra vegetable prough traditional processing. J Basic Appl Sci 2012a; 8(1): 79-84. [20] Sheikh SA Nizamani SM Mirani BN Panhwar AA Channa MJ. Effect of house hold processing on pe removal of pesticide residues in okra vegetable. J Basic Appl Sci 2012b; (1).
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