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2015 North American Chemical Residue Workshop July 22, 2015
An Update
Analysis of “table-ready” foods for ultra-trace residues oranges are peeled cabbage is boiled lasagna recipe items, e.g. tuna casserole fast food/takeout
Pesticide screening level: 0.1 ppb
Definition
FDA’s Total Diet Study – An Update
Monitor contaminants and nutrients in the food supply
Estimate exposures Acceptable Daily Intakes (ADIs) Provisional Tolerable Daily/Weekly/Monthly Intakes Tolerable Upper Intake Levels (ULs) EPA Reference Dose
Assess contaminant/nutrient trends and risk
Objectives
FDA’s Total Diet Study – An Update
Market Basket
270 items 14 age/sex group diets Analyze: Radionuclides Pesticides and Industrial Chemicals Toxic and nutritional elements
FDA’s Total Diet Study – An Update
Collection & Preparation
4 market baskets per year Collect from three cities
within a region Make “table-ready”, i.e.
cook, peel, fry, etc. Composite (3 cities)
FDA’s Total Diet Study – An Update
Church Ladies
FDA’s Total Diet Study – An Update
Analyses Over 800 P&ICs Multi-Residue Method Acid Herbicides
12 elements (5 toxic and 7 nutrient) 14 Radionuclides: 2 MBs/year Over 30,000 residues reported each year
FDA’s Total Diet Study – An Update
Pesticide Multiresidue Method (MRM)
QuEChERS Extraction
dSPE Cleanup
LC-QQQ
SPE Cleanup
GC-QQQ GCMS Fullscan
FDA’s Total Diet Study – An Update
MRM- Consolidated QuEChERS
Scope: All items Extraction: 5 g sample + 25 ml acetonitrile,
salt out, (add water to low moisture items) Cleanup:
LC: dSPE with PSA GC: SPE (25% toluene in acetone) with PSA,
GCB, and lypophylic polymer Additional dSPE with lypophylic sorbent for
items with > 6 % fat (up to 100% fat)
FDA’s Total Diet Study – An Update
MRM - Quantitative Determination
LC-MS/MS (~240) & GC-MS/MS (~210) >300 analytes Historical findings Anticipated findings Standard mixes purchased
FDA’s Total Diet Study – An Update
Qualitative Determination
FDA’s Total Diet Study – An Update
GC-MS full scan mode >800 pesticides and industrial chemicals Ions are scanned over range 45-500 m/z AMDIS deconvolution Library combines Spectra Retention indices
Analysis of Acid Herbicides Acidified QuEChERS extraction No cleanup LC-MS/MS determination uses fast pos/neg
ESI switching 35 acid herbicides Analyze 64 selected items
FDA’s Total Diet Study – An Update
Now and Then
FDA’s Total Diet Study – An Update
Metric Then Now Methods 12 2
Residues/MB ~ 550 ~ 1300 Solvent/spl ~ 1 Liter < 40 mL Spls/batch 10 20
Days/batch 14 3 Analytes ~ 500 ~ 800
Analyses/day ~400 ~ 4500 Increased efficiency > 1100 %
Now and Then
FDA’s Total Diet Study – An Update
0200400600800
100012001400160018002000
061
064
073
082
091
094
103
112
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Num
ber o
f Res
idue
s
Market Basket
Residues Reported per Market Basket
Now and Then
FDA’s Total Diet Study – An Update
108 New Pesticides Reported Since 2010 2,6-DIPN Cymoxanil Etoxazole Forchlorfenuron Methoprene Rotenone 4-CPA Cyproconazole Fenamidone Formetanate HCl Methoxyfenozide Spinetoram Abamectin Cyromazine Fenbuconazole Haloxyfop Metolachlor Spinosad Acetamiprid Diafenthiuron Fenbutatin oxide Imazamox Metrafenone Spiromesifen Acifluorfen Dichlobenil Fenoxycarb Imazapic Metribuzin Spirotetramat Ametoctradin Dichlorprop Fenpropimorph Imazapyr Moxidectin Spiroxamine Ametryn Dicrotophos Fenpyroximate, e- Imazaquin Novaluron Tebufenozide BAM Difenoconazole Fenthion Imazethapyr Oxadixyl Tebufenpyrad Bendiocarb Diflubenzuron Flonicamid Imidacloprid Penconazole Temephos Benfluralin Dimethomorph Flubendiamide Indoxacarb Pendimethalin Tetraconazole Bifenazate Diniconazole Flufenoxuron Indoxacarb Penthiopyrad Thiacloprid Carbendazim Dinotefuran Fluopyram Iprovalicarb Phenmedipham Thiamethoxam Chlorantraniliprole Dioxacarb Fluoxastrobin Isoprothiolane Phoxim Thiophanate-methyl Chlorfenapyr Dodine Fluridone Isoxaflutole Pirimicarb Triadimenol Clofentezine Emamectin Flusilazole Kresoxim-methyl Prochloraz Trichlorfon Clothianidin Epoxiconazole Flutolanil Mandipropamid Prometryn Tricyclazole Cyazofamid Ethofumesate Flutriafol Mepronil Propamocarb Triflumizole Cyflufenamid Etofenprox Fluxapyroxad Metconazole Propazine Trifluralin
Per market basket (MB) ~2000 records 1200 - 1600 residues 130 - 140 different P&ICs reported 80 % < 10 ppb 50 % ≤ 1 ppb
Residue Findings
FDA’s Total Diet Study – An Update
Residue Findings
FDA’s Total Diet Study – An Update
Pesticide % Pesticide % Boscalid 29 Chlorpyrifos methyl 9 DDE, p,p'- 21 Carbendazim 8 Piperonyl butoxide 20 Myclobutanil 8 Imidacloprid 17 Lambda-cyhalothrin 8 Malathion 16 Chlorpropham 7 Azoxystrobin 15 Thiamethoxam 7 Bifenthrin 13 Metalaxyl 7 Chlorpyrifos 12 Difenoconazole 7 Acetamiprid 11 Pyraclostrobin 7 Methoxyfenozide 11 Tebuconazole 6 Thiabendazole 10 Pyrimethanil 6 Chlorantraniliprole 10 MGK 264 6
Pesticides Found Most Frequently in Last 3 Years
Residue Findings
FDA’s Total Diet Study – An Update
THPI 48 Endosulfan II 7 Hexythiazox 2 Piperonyl butoxide 45 Thiamethoxam 7 Spiromesifen 1 Flonicamid 32 Malathion 7 Spinetoram 1 Cyprodinil 26 Acetamiprid 6 Fenbutatin oxide 0.9 Boscalid 26 Quinoxyfen 4 Thiophanate-methyl 0.8 Fludioxonil 19 Endosulfan sulfate 4 Methoxyfenozide 0.7 Novaluron 18 Carbendazim 4 Chlorantraniliprole 0.4 Fenhexamid 17 Endosulfan I 4 Cyflufenamid 0.4 Pyrimethanil 17 Myclobutanil 4 Metalaxyl 0.4 Fenpropathrin 16 Fenpyroximate 3 Clothianidin 0.3 Bifenthrin 16 Bifenazate 2 Azoxystrobin 0.2 Pyraclostrobin 13 Dichlorvos 2
Residues in strawberries (ppb)
Residue Findings
FDA’s Total Diet Study – An Update
Acid Herbicides Found in Last 5 MBs Since 2014 Herbicide Freq PPB Items Products
2,4-D 74 2 (0.3-12) 30 rice, wheat, rye, corn, brassica, okra, celery, orange, grapefruit, peanuts, peanut butter, white beans, sunflower seeds
Clopyralid 62 10 (0.4-39) 20 oats, wheat, rye, corn , rice, beets, cabbage
Imazamox 38 0.8 (0.1-5) 17 wheat, corn, oats, rice, peas, sunflower seeds Quinclorac 31 5 (0.1-28) 11 rice, wheat, corn Imazethapyr 13 0.2 (0.1-0.3) 8 rice products, peas, Triclopyr 13 0.3 (0.2-0.5) 7 rice products, peanuts 4-CPA 11 15 (0.9-26) 3 peanut products, popcorn Dicamba 6 6 (3-11) 4 wheat, corn Acifluorfen 3 1 (0.2-2) 2 rice products Haloxyfop 2 4 (0.2-8) 1 peanut butter Imazapic 1 0.2 (0.2-0.2) 1 crisped rice cereal Imazapyr 1 0.4 (0.4-0.4) 1 crisped rice cereal
Exposures
Calculate average residue level for item over selected timeframe, e.g. 1 year
Multiply by consumption rate of the item for the age/sex group
Sum the consumption of the residue for all items
Divide by the average body weight
FDA’s Total Diet Study – An Update
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
ug/k
g(bo
dy w
t)/d
ay
DDT Inf Ch2
Ch6 Ch10
F14-16 M14-16
F25-30 M25-30
F40-45 M40-45
F60-65 M60-65
F70 M70
ADI: 10 ug/kg(body wt)/day
FDA’s Total Diet Study – An Update
Exposures
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
ug/k
g(bo
dy w
t)/d
ay
Methyl Chlorpyrifos Inf Ch2
Ch6 Ch10
F14-16 M14-16
F25-30 M25-30
F40-45 M40-45
F60-65 M60-65
F70 M70
ADI: 10 ug/kg(body wt)/day
FDA’s Total Diet Study – An Update
Exposures
FDA’s Total Diet Study – An Update
Exposures
0.00
0.10
0.20
0.30
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0.60
1982
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2010
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2014
% ADI of Most Frequently Found Pesticides
DDTPiperonylBoscalidMalathionMethyl ChlorpyrifosChlorpyrifosAzoxystrobinTBZMethoxyfenozideBifenthrinImidaclopridAcetamiprid
Future Design Considerations
Revise geographic regions from 4 to 6 based upon population
Collect in two different seasons Include rural collections Specify retailers and food brands National vs regional items Collect minimum of 20 MBs @ 3 cities
per MB
FDA’s Total Diet Study – An Update
Mark Wirtz [email protected] Terry Councell [email protected]
Chris Sack [email protected]
FDA’s Total Diet Study – An Update
