PESTICIDE RESIDUES MONITORING IN FOODS >>> OUTLOOK >>> MOHAMED H. EL-SAEID, Ph.D. Chemistry & Pesticide Residue Analysis Chemistry & Pesticide Residue.

PESTICIDE RESIDUES MONITORING IN PESTICIDE RESIDUES MONITORING IN FOODSFOODS

>>> OUTLOOK >>>>>> OUTLOOK >>>

MOHAMED H. EL-SAEID, Ph.D.MOHAMED H. EL-SAEID, Ph.D. Chemistry & Pesticide Residue Analysis Chemistry & Pesticide Residue Analysis

INTRODUCTIONINTRODUCTION Several hundreds of Pesticides widely used in Several hundreds of Pesticides widely used in

the world for agricultural and other purposes the world for agricultural and other purposes such as Parathyroid, Herbicides, Fungicides, such as Parathyroid, Herbicides, Fungicides, Carbamates, OCPs & OPPs…. etc.Carbamates, OCPs & OPPs…. etc.

Using cause a residues in foods, fruits, Using cause a residues in foods, fruits, vegetables, water, soil & air.vegetables, water, soil & air.

The use of pesticides results in foods as residues, The use of pesticides results in foods as residues, consequently many healthy problems occur in consequently many healthy problems occur in the human food consumption by interact with the human food consumption by interact with the human body in different ways of disease & the human body in different ways of disease & toxic effect.toxic effect.

HAZARDOUSHAZARDOUS Deaths are estimated to be about 5.000 a year.Deaths are estimated to be about 5.000 a year. Every 17 min. a person die by pesticides Every 17 min. a person die by pesticides

poisoning.poisoning.Poisoning EffectsPoisoning Effects

@ @ PyrethroidsPyrethroids is a Neurotoxic, Nervous is a Neurotoxic, Nervous poisoning, Sodium channel closing, Itching, poisoning, Sodium channel closing, Itching, Irritation & burning sensation in the face.Irritation & burning sensation in the face.

@@ HerbicidesHerbicides is a decrease Oxygen consumption is a decrease Oxygen consumption in tissues, Carbohydrate disturb, ATPs in tissues, Carbohydrate disturb, ATPs inhibition, Liver, Kidney & Nervous system inhibition, Liver, Kidney & Nervous system damage.damage.

@ @ FungicidesFungicides is a Inhibition Enzymes containing is a Inhibition Enzymes containing SH & Metal, Allergens, Skin irritation & liver SH & Metal, Allergens, Skin irritation & liver disease.disease.

@@ CarbamatesCarbamates is a Inhibit Esterase’s & is a Inhibit Esterase’s & AChE.AChE.

@ @ OCPsOCPs is a Carcinogenic, Liver damage, is a Carcinogenic, Liver damage, Increase in Alkaline Phosphaatase & Increase in Alkaline Phosphaatase & Aldolase activity, Interact with Aldolase activity, Interact with Drugs Drugs & Hormones, damaged of & Hormones, damaged of Central Central Nervous s., Disturb Protein & Lipid Nervous s., Disturb Protein & Lipid

functions.functions.

@@ OPPsOPPs is a Inhibit AChE, Acute intoxica- is a Inhibit AChE, Acute intoxica- tion symptoms, Eye disease, tion symptoms, Eye disease, Respiratory system disease, Respiratory system disease, Gastrointestinal system disease & Gastrointestinal system disease & Central Nervous system disease.Central Nervous system disease.

What We have to doWhat We have to do…..….. To protect the food customers>>>To protect the food customers>>>>> Discovered the a new, rapid & quick >> Discovered the a new, rapid & quick techniques & methodology for pesticide techniques & methodology for pesticide

residues. residues. EXTRACTIONEXTRACTION Supercritical Fluid Ext. (SFE)Supercritical Fluid Ext. (SFE) Microwave Solvent Ext. (MSE) Microwave Solvent Ext. (MSE) ** Accelerated solvent Ext. (ASE) Accelerated solvent Ext. (ASE) ** Sonication Ext. (SAE) Sonication Ext. (SAE) ** Solid Phase Ext. (SPE) Solid Phase Ext. (SPE) ** Pressurized Solvent Ext. (PSE) Pressurized Solvent Ext. (PSE) ** Purge trap & Purge HeadspacePurge trap & Purge Headspace

**((EPA &EPA & FDA)FDA)

SFE & MSE hasSFE & MSE has Potential advantages than conventional extraction. Potential advantages than conventional extraction.

Methods.Methods. Reduced time.Reduced time. Superior recovery.Superior recovery. Reduction in solvent usage.Reduction in solvent usage. No cleanup.No cleanup. Safe.Safe. SFE can be coupled directly with SFC.SFE can be coupled directly with SFC. MSE has proven to be safe alternative to MSE has proven to be safe alternative to

conventional organic solvent extraction.conventional organic solvent extraction. High ability as Food and soil extraction techniques.High ability as Food and soil extraction techniques.

SFESFE MSEMSE

No cleanup Need for both extraction No cleanup Need for both extraction methods.methods.

No cleanup Need for both extraction methods.No cleanup Need for both extraction methods.

ASEASE

SPESPE

DETERMINATIONDETERMINATION

Supercritical Fluid Chromatography (SFC)Supercritical Fluid Chromatography (SFC) GC-ECD/NPD/FID/FPD HPLC-UV/FLGC-ECD/NPD/FID/FPD HPLC-UV/FL** Capillary Electro Chromatography (CEC)Capillary Electro Chromatography (CEC) ELISAELISA**

LC/MS & LC-MS/MSLC/MS & LC-MS/MS** GC-MS & GC-MS/MSGC-MS & GC-MS/MS**

**((EPAEPA, , FDA & AOAC )FDA & AOAC )

SFCSFC Separation techniques used critical points & Separation techniques used critical points &

carrier gases of COcarrier gases of CO2 2 With modifiers.With modifiers. COCO22 is a safe gas to use. is a safe gas to use. Become increasingly apparent in last several Become increasingly apparent in last several

years.years. Complements GC & HPLC, it can be analyze Complements GC & HPLC, it can be analyze

different molecular weights without drivatization. different molecular weights without drivatization. Increase the analysis speed 10 times.Increase the analysis speed 10 times. Wider range of detectors, polarity & sensit.Wider range of detectors, polarity & sensit. Can be coupled with SFE for many groups of Can be coupled with SFE for many groups of

pesticides residues.pesticides residues. Highly sensitivity.Highly sensitivity.

SFCSFC

Enzyme Linked Immunosorbent Assay {ELISA} isEnzyme Linked Immunosorbent Assay {ELISA} is The EnviroGard Plate Kit is a quantitative The EnviroGard Plate Kit is a quantitative

laboratory test for the detection of pesticide laboratory test for the detection of pesticide residues in water, soil and foods uses polyclonal residues in water, soil and foods uses polyclonal antibodies which bind Ps-enzyme conjugate for antibodies which bind Ps-enzyme conjugate for a limited number of antibody binding sites a limited number of antibody binding sites inside of the wells.inside of the wells.

EPAEPA, , FDAFDA,, AOAC AOAC and and Codex methodsCodex methods.. Rapid (less than Rapid (less than 55 min.55 min.) for 84 samples .) for 84 samples . Inexpensive, portable & can be used to Inexpensive, portable & can be used to

evaluate many samples at the same time.evaluate many samples at the same time. Simple & sensitive (Simple & sensitive (0.001 ppb0.001 ppb).). No solvent disposal.No solvent disposal.

Plate Plate MechanismMechanism

FACTSFACTS DETERMINATIONDETERMINATION

• By modified SFC/UVD new techniques can be By modified SFC/UVD new techniques can be determined 8 Pyrethroids, 8 Herbicides, 7 Fungicides, determined 8 Pyrethroids, 8 Herbicides, 7 Fungicides, 12 Carbamates in 25, 10, 12 & 30 min only.12 Carbamates in 25, 10, 12 & 30 min only.

• By modified HPLC/FD technique can be determined 8 By modified HPLC/FD technique can be determined 8 Carbamates in 55min.Carbamates in 55min.

• By modified GC/ECD new techniques can be By modified GC/ECD new techniques can be determined 16 OCPs in 28 min only.determined 16 OCPs in 28 min only.

• By modified GC/FPD new techniques can be By modified GC/FPD new techniques can be determined 25 OPPs in 66 min only.determined 25 OPPs in 66 min only.

• MDL were ranged from 0.0001 – 0.02 ppm.MDL were ranged from 0.0001 – 0.02 ppm.

ExtractionExtraction & Determination Time (min.) & Determination Time (min.) Supercritical Fluid Ext. (SFE)Supercritical Fluid Ext. (SFE) 15.0 15.0 Microwave Solvent Ext. (MSE) Microwave Solvent Ext. (MSE) 5.0 5.0 Accelerated solvent Ext. (ASE) 20.0Accelerated solvent Ext. (ASE) 20.0 Sonication Ext. (SAE)Sonication Ext. (SAE) 30.0 30.0 Solid Phase Ext. (SPE)Solid Phase Ext. (SPE) 15.0 15.0 Pressurized Solvent Ext. (PSE) 15.0Pressurized Solvent Ext. (PSE) 15.0 Purge trap & Purge Headspace 25.0Purge trap & Purge Headspace 25.0 SFC SFC 10.0 10.0 ELISA ELISA 2.0 2.0 GCsGCs 30.0 30.0 HPLCHPLC 50.0 50.0 LC/MS 40.0 LC/MS 40.0 GC-MS 45.0GC-MS 45.0

RECOVERY %RECOVERY %

• 8 Pyrethroids 93-103%.8 Pyrethroids 93-103%.

•8 Herbicides 91-102%8 Herbicides 91-102%

•7 Fungicides 90-107%7 Fungicides 90-107%

•12 Carbamates 92-101%12 Carbamates 92-101%

•8 Carbamates 88-103%8 Carbamates 88-103%

•16 OCPs 96-105% 16 OCPs 96-105%

•25 OPPs 97 –106%25 OPPs 97 –106%

•AOSC dtermined 19 pesticides from 76 by NT.AOSC dtermined 19 pesticides from 76 by NT.

CONCLUSIONCONCLUSIONNEW EXTRACTION METHODOLOGY BY SFE, NEW EXTRACTION METHODOLOGY BY SFE, ASE, SONICATION, SPE &MSE WAS ASE, SONICATION, SPE &MSE WAS SUCCESSFUL FOR MORE THAN 74 PESTICIDE SUCCESSFUL FOR MORE THAN 74 PESTICIDE RESIDUES IN FOODS.RESIDUES IN FOODS.NEW DETERMIATION METHODOLOGY BY NEW DETERMIATION METHODOLOGY BY SFC, HPLC& GC WAS SUCCESSFUL FOR 76 SFC, HPLC& GC WAS SUCCESSFUL FOR 76 PESTICIDE RESID UES IN FOODS.PESTICIDE RESID UES IN FOODS.APPLICATION OF NEW METHODOLOGY APPLICATION OF NEW METHODOLOGY OBTAINED TO PROTECT THE FOOD OBTAINED TO PROTECT THE FOOD CUSTOMERS.CUSTOMERS.ELISA technique coupled with SFE & MSE is less ELISA technique coupled with SFE & MSE is less time consuming, high recovery% and more sensitive time consuming, high recovery% and more sensitive with lower detection limit of Pesticide residues in with lower detection limit of Pesticide residues in foods.foods.

RECOMENDATIONSRECOMENDATIONS MODERN UNITS AND LABS WITH MODERN UNITS AND LABS WITH

NEW TECH. FORNEW TECH. FOR

» RESEARCHESRESEARCHES» DATA BASEDATA BASE» MARKETS ( FOODS, WATERS, MARKETS ( FOODS, WATERS, SOILS……etc.SOILS……etc.» ANALYTICAL QC/QA ACCRED.ANALYTICAL QC/QA ACCRED.» PESTICIDE RESIDUE MAPS. PESTICIDE RESIDUE MAPS.

PESTICIDE RESIDUES MAPSPESTICIDE RESIDUES MAPS

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