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Evaluation of QuEChERS Application on FIFRA Misuse Samples
Rich Buhl, Erin Sloan, and Yoko Johnson
51st NACRW July 20-23, 2014
- Report from a Pesticide Workshop Hosted by a State Laboratory -
Overview
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1. State FIFRA Laboratories – Our Mission
2. Challenges Unique to Us
3. Countermeasures
● EPA Region 5 Workshop
a class: QuECHERS, FIFRA misuse, and vegetation
● Mutual Aid Agreement
● Regional Formulation Lab
● FIFRA Check Sample Program
4. Another Helpful Tool
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State FIFRA Laboratory
Cooperative agreement with EPA and States
• Formulation
• Misuse Investigation
51st NACRW July 20-23, 2014
In Minnesota;
Department of Agriculture has the sole regulatory authority
over the terrestrial application of pesticides.
Federal Insecticide, Fungicide, and Rodenticide Act
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Challenges in FIFRA Work
51st NACRW July 20-23, 2014
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Challenges in FIFRA Work
Management Level
“ …It was suggested that communication within the states
and from State Lead Agencies to EPA and back could be
improved in this area (State Laboratories) to mutual
benefit.
…Several participants suggested that EPA sponsor more
lab director meetings to discuss all phases of laboratory
functions, needs etc. It was recommended that EPA
consider holding such a meeting in conjunction with the
Spring AAPCO meeting. EPA agreed to explore this
possibility”
Summary of Major Issues Discussed at the Chemistry Workshop
September 28 & 29 1989
St. Louis, MO
51st NACRW July 20-23, 2014
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Countermeasures
Management Level
• Association of American Pesticide Control Officials
(AAPCO) Lab Directors Meeting
• EPA Region 5 Laboratory Directors Meeting
Laboratory Workshop (since 1997)
Mutual Aide Agreement
Regional Formulation Laboratory
FIFRA Check Sample Program
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Challenges in FIFRA Work
Analyst Level
Test requests are variable and unpredictable.
Analyte/matrix combination
Sample load
No tolerance.
No available methods that meet the complete
needs.
Client often needs the results as fast as possible.
51st NACRW July 20-23, 2014
No commercially
available PT for
vegetation matrix
QuEChERS could help but…
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Little has been reported on using QuEChERS for pesticide
metabolites and degradates in vegetation matrices.
But we need to look for
metabolites for misuse
investigation,
monitoring etc.
40 CFR
Challenges in FIFRA Work
Analyst Level
No need to analyze
Mesotrione MBNA &
AMBA for food
tolerance work
51st NACRW July 20-23, 2014
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Countermeasures
Analyst Level EPA R5 Workshop: April 7-11, 2014 St. Paul Minnesota
51st NACRW July 20-23, 2014
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EPA R5 Workshop: April 7-11, 2014 St. Paul Minnesota
Clethodim Methomyl Sulfoxide
Clethodim Sulfoxide Myclobutanil
Diflufenzopyr Rimsulfuron
Flumetsulam Saflufenacil
Imazethapyr Saflufenacil 307
Mesotrione Saflufenacil 308
Mesotrione AMBA Tembotrione
Mesotrione MNBA Thiophanate
Metconazole Topramezone
Methomyl Trifloxystrobin
Methomyl Sulfone Trifloxystrobin Acid
[Analytes]
51st NACRW July 20-23, 2014
Class #2
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EPA R5 Workshop: April 7-11, 2014 St. Paul Minnesota
[Extraction] 5 g of sample with 10 mL acetonitrile
a. 4 g MgSO4; 1 g NaCl; 1 g NaCitrate; 0.5 g disodium
citrate sesquihydrate
b. 4 g MgSO4; 1 g NaCl
c. 6 g MgSO4; 1.5 g NaAcetate
[Cleanup] approximately 5 mL of extract
a) No cleanup
b) X4 dilution
c) 150 mg PSA and 900 mg MgSO4
d) 150 mg C18EC and 900 mg MgSO4
12 types of extracts
n=12: Twelve students
*4 students per class (48 injections per day) x 3 days
51st NACRW July 20-23, 2014
Class #2
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It is not crazy but it is a lot!
51st NACRW July 20-23, 2014
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EPA R5 Workshop: April 7-11, 2014 St. Paul Minnesota
51st NACRW July 20-23, 2014
[Result] Average recoveries [%], n=12
a. citrate b. original c. acetate Compound a) b) c) d) a) b) c) d) a) b) c) d)
Clethodim 27 35 44 26 26 37 47 23 21 39 32 18
Clethodim Sulfoxide 31 56 21 30 32 61 24 33 39 68 29 43
Diflufenzopyr 86 102 10 86 78 92 14 67 66 75 3 42
Flumetsulam 61 122 29 74 66 134 32 78 55 120 19 73
Imazethapyr 39 58 4 75 38 58 6 40 28 44 3 27
Mesotrione 47 89 8 56 43 89 10 51 42 83 6 51
Mesotrione AMBA 52 110 - 49 45 124 6 41 18 - - 10
Mesotrione MNBA 47 - 62 59 44 - 58 57 47 - - 51
Metconazole 24 33 58 26 23 33 58 27 30 43 47 29
Methomyl 51 68 75 55 54 75 75 60 57 77 75 65
Methomyl Sulfone 37 59 55 41 42 117 51 47 53 76 63 60
Methomyl Sulfoxide 99 408 116 88 85 382 104 82 82 397 102 87
Myclobutanil 39 56 74 42 40 61 76 42 43 64 70 46
Rimsulfuron 61 61 20 47 66 71 26 53 69 66 8 50
Saflufenacil 60 96 53 70 54 95 62 59 75 120 31 88
Saflufenacil 307 111 238 34 131 121 249 43 145 128 253 29 147
Saflufenacil 308 85 120 16 102 91 128 23 106 85 118 8 103
Tembotrione 42 67 6 40 43 73 11 40 47 76 7 44
Thiophanate 23 16 20 15 23 17 19 15 20 15 18 13
Topramezone 38 67 5 27 40 67 7 34 41 75 5 42
Trifloxystrobin 20 27 38 22 18 26 39 24 27 42 34 23
Trifloxystrobin Acid 98 421 104 94 98 416 102 90 87 411 102 94
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EPA R5 Workshop: April 7-11, 2014 St. Paul Minnesota
Larisa Reonova
EPA R5
My result is
going to be
the Best!
Graduation
Small class size
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Builds familiarity and trust among analysts.
Opens communication lines among analysts.
Builds relationships with Regional EPA staff.
Lab issues are heard at the regional level.
Helps hosting lab build teamwork.
Analysts at hosting lab become more proud of
what they do.
Countermeasures
Analyst Level
Benefits from EPA R5 Workshop
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Countermeasures
National Level
EPA Pesticide Regulatory Education Program
(PREP) Course – since 1990 Provides pesticide-related training for senior management, senior
scientists, and supervisors and managers of pesticide regulatory
programs from state/tribes and U.S. territories working under FIFRA
Cooperative Agreements with EPA.
Association of American Pesticide Control Officials
(AAPCO) Lab Directors Meeting
EPA National Pesticide Residue Analytical Workshop
51st NACRW July 20-23, 2014
Another helpful tool for analysts
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Poster No.37
Q&A Handbook for Pesticide Residue Analysis
by the Pesticide Society of Japan
101 Questions: We translated them all!
51st NACRW July 20-23, 2014
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Thank you!
51st NACRW July 20-23, 2014
EPA Region 5 for supporting the workshop
The workshop participants;
Larisa Leonova (EPA R5)
Meghan Dunn (EPA R5)
Students from the EPA R5 States
Technical Questions to: [email protected]