Fengshou Dong Ph.D. Institute of Plant Protection Chinese Academy of Agricultural Sciences, 20 February 2012

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1 The pesticide residue changes during food processing and storage Fengshou Dong Ph.D. Institute of Plant Protection Chinese Academy of Agricultural Sciences, 20 February 2012

2 Outline. Introduction. Effects of storage on pesticide residues. Effects of processing on pesticide residues. Conclusion Ⅴ. Future scope

3 Part Ⅰ Introduction Food safety

4 Part Ⅰ Introduction Pesticide is any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating g any pest. Pesticide includes herbicides, fungicides, insecticides, or any other substance used to control pests.

5 Part Ⅰ Introduction The pesticide residues, left to variable extent in the food materials after harvesting, are beyond the control of consumer and have deleterious effect on human health. The presence of pesticide residues is a major bottleneck in the international trade of food commodities. The localization of pesticides in foods varies with the nature of pesticide molecule, type and portion of food material and environmental factors. The food crops treated with pesticides invariably contain unpredictable amount of these chemicals, therefore, it becomes imperative to find out some alternatives for decontamination of foods. MRL: Maximum Residue Limits

6 Part Ⅰ Introduction Raw Agricultural Commodity (RAC): Any food in its raw or natural state, including all fruits that are washed, colored, or otherwise treated in their unpeeled natural form prior to marketing. MRLs are set on unwashed, unpeeled commodities

7 Part Ⅰ Introduction Processed Agricultural Commodity (PAC): raw agricultural commodity that has been subject to processing, like tomato paste, wine, and orange juice.

8 Part Ⅰ Introduction decrease Increase Drying, concentration metabolites Peeling, washing More toxic substance The effect of processing

9 Part Ⅰ Introduction PF = Processing i Factor t = Proportional amount by which residues change when processed PF residue concentration in the processed commodity (mg Kg residue concentration in the raw commodity (mg Kg 1 ) -1 ) PF<1:REDUCTION FACTOR PF>1: CONCENTRATION FACTOR

10 Part Ⅰ Introduction How Do Pesticides Get Into Processed Foods? Direct Treatment of raw commodities prior to harvest or after harvest treatment of storage facilities for processed foods This talk will focus on the fate of pesticide residues when treated raw commodities are processed.

11 Part Ⅰ Introduction Determine whether residues concentrate or reduce when raw commodity is processed Determine whether MRLs are needed in the processed commodities Refine dietary exposure assessment

12 Part Ⅱ Effects of storage on pesticide residues Proper storage of unprocessed food of plant origin includes maintaining at appropriate temperatures, away from light, under the proper percentage of humidity and in such a way to keep it clean and safe prior the further management of the product. Temperature control cold storage

13 Part Ⅱ Effects of storage on pesticide residues 1 Pesticide volatilization Temperature 2 3 Pesticide penetration Pesticide metabolism 4 Certain microbial growth 5 The reduction of moisture loss

14 Part Ⅱ Effects of storage on pesticide residues Grains are frequently stored long term (3-36 months) at ambient temperatures in bulk silos where insecticides may be applied post-harvest to reduce losses from storage pests. Grain based foods therefore have the potential to be a major source of residues in the diet for these insecticides.

15 Part Ⅱ Effects of storage on pesticide residues organophosphates pesticide nature malathion pirimiphos methyl chlorpyrifos methyl type of applied formulation storage temperature and humidity (Uygun et al., 2005; Uygun et al., 2007)

16 Part Ⅱ Effects of storage on pesticide residues Most high moisture unprocessed foods must be held in chillers or refrigerators (0 to 5 ) for short to medium storage or deep frozen (-10 to -20 ) for longer periods.

17 Part Ⅱ Effects of storage on pesticide residues 1 Pesticide volatilization 2 Slow acidic hydrolysis Studies on a variety of pesticides on whole food-stuffs under cool or frozen storage often have shown that residues are stable or degraded slowly. (Athanasopoulos et al., 2000; Athanasopoulos et al., 2005)

18 Part Ⅲ Effects of processing on pesticide residues juicing washing processing of food commodities generally implies the transformation of the perishable raw commodity to value-added product. Wine making Processing Peeling cooking comminution

19 Part Ⅲ Effects of processing on pesticide residues Washing: The preliminary step in both household and commercial food preparation Rinesability

20 Part Ⅲ Effects of processing on pesticide residues the location of the residue The effectiveness of washing the age of the residue the water solubility of the pesticide the temperature and type of wash

21 Part Ⅲ Effects of processing on pesticide residues Peeling is an important step in the processing of most fruits and vegetables. Chemical peeling Mechanical peeling peeling steam peeling freeze peeling (Toker & Bayindirli, 2003)

22 Part Ⅲ Effects of processing on pesticide residues

23 Part Ⅲ Effects of processing on pesticide residues juicing: Commercial juicing operations generally use whole fruit. The residue levels in juices from fruits or vegetables are generally reduced by % and their reduction depends on the partitioning ratio of the pesticide between the fruit skin, pulp and the juice The pulp or pomace by-products, which h often include the skin, retain a substantial ti residues. Clarification by filtration or centrifugation in juice processing may further eliminate pesticide residues retained in suspended particles; juice concentration by vacuum may concentrate the pesticides in juice product.

24 Part Ⅲ Effects of processing on pesticide residues Comminution: comminution of tissues in chopping, blending etc. leads to release of enzymes and acids which may increase the rate of hydrolytic and other degradative processes on residues. For example, fine chopping of crop samples leads to rapid degradation of EBDC fungicide. However most pesticides are relatively stable in acidic tissue. S. Kontoua etc. 2004; Food Additives and Contaminants

25 Part Ⅲ Effects of processing on pesticide residues thiodicarb carbosulfan dioxacarb Acid sensitive pesticide EBDCs pymetrozine benfuracarb

26 Part Ⅲ Effects of processing on pesticide residues Cooking: the act of preparing food for eating by the application of heat. Pesticide residues might be vaporized, hydrolyzed and thermal degraded during cooking. TIME SYSTEM WATER CONDITION MOISTURE TEMPERATURE

27 Part Ⅲ Effects of processing on pesticide residues Wine making: pesticide residue present on grapes often remain adsorbed in lees at relevant levels, and it could transferred to the wine in low percentages after fermentation. Mainly on the initial partition of a pesticide residue between the must and lees. Wine making

28 Part Ⅲ Effects of processing on pesticide residues Drying: The Drying is the oldest method of preserving food. As compared with other methods, drying is quite simple. Food can be dried in several ways, for example, by the sun or in an oven or a food dryer can also be used. Drying has been found to reduce the pesticide residues considerably. Sun Drying

29 Part Ⅲ Effects of processing on pesticide residues METABOLITES : the metabolites of pesticide during the food processing is a hot issue, particularly those involving use of heat or chemicals. Although no examples are available of pesticides where food processing has resulted in the production of new metabolites, the proportions of various metabolites may change from those found in field or laboratory studies on whole plants.

30 Part Ⅲ Effects of processing on pesticide residues Degradation of acephate and its metabolite methamidophos in rice during processing and storage Commercial processing Simulating Home processing

31 Part Ⅲ Effects of processing on pesticide residues Paddy rice Drying Hulling polishing Name Aceph ate Metha midop hos Raw Rice Brown Rice Brown Rice Brown Rice Polish rice hull rice hull rice hull rice bran ed rice 3.71± 11.7± 0.92± 9.42±0 0.84± 8.92± 0.8±0 1.26± ± ± ± ± ± ± ± ± ± ±0.0 2 Amount of acephate and methamidophos residues (mg kg -1 ) recovered from rice grains after various commercial processes (mean ± SD). Treatment Acephate Methamidophos Polished rice 0.51± ±0.02 Water from washing First time 0.084± ±0.002 Second time 0.024± ± Third time 0.022± ± Washed polished rice 0.33± ±0.008 Cooked polished rice 0.082± ±0.006 Distillate 0.078± ±0.002 Amount of acephate and methamidophos residues (mg kg -1 ) recovered from rice samples after home processes (mean ± SD).

32 Part Ⅲ Effects of processing on pesticide residues Raw rice Brown rice Polished rice Cooked rice

33 Part Ⅲ Effects of processing on pesticide residues C 0229t t = e t Conce entration (mg g/kg) C t = e t Acephate Methamidophos Time (days) The methamidophos was found to be more persistent than acephate

34 Part Ⅲ Effects of processing on pesticide residues Concentra ation (mg/kg) Concentration (m mg/kg) Time (min) Time (min) Washing Washing Concentration of acephate after washing Concentration of methamidophos h after washing

35 Part Ⅲ Effects of processing on pesticide residues Determination of difenoconazole residue in tomato during home canning by UPLC-MS/MS

36 Part Ⅲ Effects of processing on pesticide residues peeling juicing sterilization simmering

37 Part Ⅲ Effects of processing on pesticide residues Sample Concentration (mg kg -1 ) difenoconazole Processing factor Raw tomatoes Washed tomatoes Tomato pulp Tomato skin Tomato puree Tomato juice Tomato seeds LOD - Tomato paste Canned tomato paste Table: Residue levels of difenoconazole in raw tomatoes and its products (mg kg -1 ) and experimental processing factors.

38 Part Ⅲ Effects of processing on pesticide residues 7 6 concent tration (mg kg-1) Raw Washing Peeling Juicing Concentration Sterilization

39 Part Ⅲ Effects of processing on pesticide residues (IF: 2.812)

40 Part Ⅳ Conclusion Washing (tap water) 22-60% Juicing 73-91% Wine making % Peeling % Critical Reviews in Food Science and Nutrition, 51: (2011)

41 Part Ⅴ Future scope It is necessary to optimize the processing techniques with regard to pesticide residue dissipation and nutrient content. Further the bioavailability of nutrients in pesticide residue contaminated tdfood needs to be investigated tdas this aspect has not been explored as yet. Detailed studies on the fate of metabolites during food processing are lacking for most of the pesticides. Some pesticides MRLs should be set on processed agricultural commodity to perfect the dietary exposure assessment for human health.

42 Thanks for your atten

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