Propargite (PC 097601)
MRIDs 50593501/50393501
Analytical method for propargite and its metabolite TBPC in soil
Reports:
ECM: EPA MRID No.: 50593501. Batorewicz, W. 2003. Validation of the
Analytical Method for the Determination of Propargite (Omite ®) and the
Metabolite TBPC in Soil. Report prepared, sponsored and submitted by
Crompton Corporation (a Legacy Company of MacDermid Agricultural
Solutions, Inc., c/o Arysta LifeScience North America, LLC), Middlebury,
Connecticut. Crompton Corporation Study No.: 2002-061. 105 pages. Final
report issued April 30, 2003.
Document No.
Guideline:
Statements:
Classification:
ILV: EPA MRID No.: 50393501. Zhang, L. and K.H. Martin. 2017.
Independent Laboratory Validation of Methods for the Determination of
Propargite and its Metabolite TBPC in Soil by GC/MS. Report prepared by
EAG Laboratories™, EAG, Inc., Easton, Maryland; sponsored and submitted
by MacDermid Agricultural Solutions, Inc., c/o Arysta LifeScience North
America, LLC, Cary, North Carolina. EAG Project No: 443C-127. Sponsor
Study No.: 2016-004. 57 pages. Final report issued September 18, 2017.
MRIDs 50593501 & 50393501
850.6100
ECM: The study was conducted in compliance with USEPA FIFRA Good
Laboratory Practice (GLP) standards, with the exception that the computer
system was not fully validated (40 CFR 160; p. 3 of MRID 50593501). Signed
and dated Data Confidentiality, GLP, Quality Assurance, and Certification of
Authenticity statements were provided (pp. 2-5).
ILV: The study was conducted in compliance with USEPA FIFRA and OECD
GLP standards (p. 3 of 50393501). Signed and dated Data Confidentiality,
GLP and Quality Assurance statements were provided (pp. 2-4). The statement
of authenticity was not included.
This analytical method is classified as acceptable. The method generally
satisfied the repeatability and reproducibility criteria, with RSDs < 20% and
mean recoveries in the range of 70 - 120%, except the ILV linearity was not
satisfactory for TBPC analysis and the ECM linearity was not satisfactory for
propargite or TBPC analysis.
PC Code:
EFED Final
Reviewer:
CDM/CSS-
Dynamac JV
Reviewers:
097601
William Gardner, Ph.D.,
Environmental Scientist
Teresa Nelis,
Environmental Scientist
Lisa Muto, M.S.,
Environmental Scientist
Signature: Gardner
Date: 11/19/18
Signature:
Date: 10/8/18
Signature:
Date: 10/15/18
William Gardner
Date: 2018.11.19
1S2S W OS'00'
This Data Evaluation Record may have been altered by the Environmental Fate and Effects Division
subsequent to signing by CDM/CSS-Dynamac JV personnel. The CDM/CSS-Dynamac Joint Venture
role does not include establishing Agency policies.
Page 1 of 11
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
Executive Summary
The analytical method, Crompton Corporation Study No. 2202-061, is designed for the quantitative
determination of propargite and its metabolite TBPC in soil at the stated LOQ of 0.01 mg/kg using
GC/MS. The LOQ is lower than the lowest toxicological level of concern (1.22 a.i. mg/kg; USEPA
2014) in soil for the two analytes. The ECM validated the method for the two analytes using one
characterized sandy loam soil matrix and incorporated an internal standard for analysis and
quantification. The ILV validated the method using one characterized loamy sand soil matrix and
incorporated an internal standard for analysis only. It could not be determined if the ILV was
provided with the most difficult matrix with which to validate the method. Additionally, more than
one soil matrix would need to be included in an ILV to cover the range of soils used in the
terrestrial field dissipation studies. In the ECM and ILV, three ions were monitored for propargite
and TBPC, but only the response of the primary ion was quantified. The number of trials in the ILV
was not specified, but the reviewer assumed that the method was validated in the first trial based on
communications between the ILV and the Study Sponsor. The ECM was performed by the ILV
with only insignificant modifications to the analytical equipment and the identification of two
critical steps: segregation of matrix blank samples and matrix fortification samples on the N-EVAP
evaporator, and the importance of transferring the exact specified amount of the hexane extract to
clean glass tubes after extraction. All ILV and ECM data regarding repeatability, accuracy,
precision, and specificity were satisfactory for propargite and TBPC. ECM linearity was not
satisfactory for propargite or TBPC analysis in sandy loam soil matrix; ILV linearity was not
satisfactory for TBPC analysis in loamy sand soil matrix.
Table 1. Analytical Method Summary
Analyte(s)
by
Pesticide
MRID
EPA
Review
Matrix
Method Date
(dd/mm/yyyy)
Registrant
Analysis
Limit of
Quantitation
(LOQ)
Environmental
Chemistry
Method
Independent
Laboratory
Validation
Propargite
505935011
503935012
Soil
30/04/2003
MacDermid
Agricultural
Solutions, Inc.
c/o Arysta
Life Science
North America
GC/MS
0.01 mg/kg
TBPC
1 In the ECM, the sandy loam soil (Batch July-01; 77.25% sand, 13.41% silt, and 9.34% clay, pH 6.18 in CaCk 1.15%
organic carbon) obtained from Stolpe, Germany was characterized by RCC Ltd., Itingen, Switzerland (p. 15,
Appendix II, p. 58 of MRID 50593501). USDA soil texture classification was not specified, but particle size
distributions corresponded to USDA soil particle size distributions.
2 In the ILV, the loamy sand soil (PD-SOIL-PF-O-6"; 80% sand, 14% silt, and 6% clay, pH 6.2 in 1:1 soil:water ratio,
0.88% organic matter Walkley-Black) obtained from North Dakota was characterized by Agvise Laboratories,
Northwood, North Dakota (USDA soil texture classification; p. 12, Appendix II, p. 48 of MRID 50393501).
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
I. Principle of the Method
Soil (10 g) was fortified (100 |iL) with the appropriate fortification solution, as necessary, in a 50-
mL plastic centrifuge tube (pp. 15, 18, Appendix IV, pp. 85-87 of MRID 50593501). The sample
was extracted with 25 mL of acetonitrile, vortexed (30 seconds), sonicated (10 minutes) and
centrifuged (5,000-6,000 rpm for ca. 10 minutes); the supernatant was decanted into a 50 mL
centrifuge tube, and the extraction process was repeated. The supernatants were combined and
evaporated in an N-EVAP evaporator (ca. 50°C water bath) to a 5 mL volume and transferred to a
15 mL polypropylene centrifuge tube; the 50 mL centrifuge tube was rinsed into the 15 mL
centrifuge tube with 0.5 mL of acetonitrile. The 15 mL centrifuge tube was placed on the N-EVAP
evaporator under a stream of nitrogen, the supernatant reduced to a 1 mL volume, 5 mL of 10%
NaCl and 5 mL of hexane added to the extract, and the extract was vortexed (30 seconds) and
centrifuged (2 minutes). Using a disposable plastic pipette, 4 mL of the upper hexane phase was
transferred to a new 15 mL polypropylene centrifuge tube, the hexane extraction step repeated, and
5 mL of the upper hexane phase from the second hexane extraction was added to the first hexane
extract. Internal standards were added to the hexane extract. For samples fortified at the LOQ, the
hexane extract containing the added internal standards was reduced under a stream of nitrogen to 1
mL; for samples fortified at lOxLOQ, hexane was added to the extract containing the added internal
standards to bring the total volume to 10 mL. Aliquots of the supernatant were transferred to an
autosampler vial for analysis by GC/MS (mass selective detector).
Samples were analyzed for propargite and TBPC using an Agilent 5890 capillary GC equipped with
an Agilent 5972 MSD and a J & W DB-1 capillary column (30 m x 0.25 mm i.d. x 0.25 |im film
thickness), a temperature gradient of 210°C injector, 60°C initial temperature, 10°C/minute ramp
rate and 295°C final temperature, and selective ion monitoring (SIM) mode (pp. 12, 15, 19-20,
Appendix IV, pp. 82, 86-87 of MRID 50593501). Injection volume was 2 |iL. Propargite was
identified using three ions; one for quantitation (Q) and two for confirmation (C): m/z 350 (Q), m/z
173 (CI) and m/z 150 (C2); the propargite internal standard was monitored at m/z 173. TBPC was
identified using three ions: m/z 248 (Q), m/z 150 (CI) and m/z 233 (C2); the TBPC internal standard
was monitored at m/z 150. Approximate retention times were ca. 22.2 and 21.6 minutes for
propargite and the propargite internal standard, respectively, and ca. 17.7 and 17.1 minutes for
TBPC and the TBPC internal standard, respectively.
The ILV performed the ECM methods for each analyte as written, except for substitution of glass
centrifuge tubes and glass pipettes for plastic, segregation of the matrix blank and low-level
fortification samples on the N-EVAP evaporator, and modifications to the analytical equipment (pp.
14-15; Tables 1-2, pp. 20-22, Appendix IV, p. 55 of MRID 50393501). The ILV transferred the
reduced acetonitrile extracts into 15-mL glass centrifuge tubes; and glass pipettes were used to
transfer the upper hexane phases into clean 15-mL glass centrifuge tubes (p. 14; Table 1, p. 20 of
MRID 50393501). The ILV reported the following critical steps: 1) segregating matrix blank
samples from matrix fortification samples on the N-EVAP to minimize the potential for cross
contamination on the N-EVAP evaporator; and 2) for the step in which hexane extracts are to be
transferred to clean glass tubes after extraction, the ILV indicated that the volume transferred for
each sample must be the same as specified in the ECM method (Appendix IV, p. 55). The ILV
GC/MS parameters, injection volume, and quantitation ion and confirmation ion analysis for
propargite and TBPC were the same as those of the ECM. The ILV GC/MS instruments were
similar but were newer models compared to those of the ECM: samples were analyzed for
propargite in the ILV using an Agilent 7890 capillary GC equipped with an Agilent 5975 MSD and
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
an Agilent 122-0132DB-1MS column (30 m x 0.25 mm i.d. x 0.25 |im film thickness). ILV
reported retention times were similar to the ECM retention times and were 22.0 and 21.5 minutes
for propargite and the propargite internal standard, respectively, and 17.6 and 17.0 minutes for
TBPC and the TBPC internal standard, respectively; propargite and TBPC were monitored at the
same primary and confirmation ions as the ECM.
In the ECM and ILV, the Limit of Quantification (LOQ) was 0.01 mg/kg for propargite and TBPC
in soil (p. 26 of MRID 50593501; p. 13 of MRID 50393501). In the ECM and ILV, the Limit of
Detection (LOD) for propargite and TBPC was 0.005 mg/kg (p. 26 of MRID 50593501; p. 14 of
MRID 50393501).
II. Recovery Findings
ECM (MRID 50593501): Mean recoveries and relative standard deviations (RSDs) for GC-MS
analysis using the quantitation ion were within guidelines (mean 70-120%; RSD <20%) for
propargite and TBPC at fortification levels of 0.01 mg/kg (LOQ) and 0.10 mg/kg (lOxLOQ) in one
soil matrix (Tables I-IV, pp. 29-32; Appendix III, pp. 61-64). For the first set of lOxLOQ propargite
samples, two out of five recoveries for propargite were greater than 110%; as a result, the analysis
was repeated; the high recoveries were attributed to an error in spiking of the two samples (p. 25).
Data for the second attempt at lOxLOQ were reported for propargite. Analytes were identified using
three ions, but recovery results were only reported for the quantitation ion. The sandy loam soil
(Batch July-01; 77.25% sand, 13.41%) silt, and 9.34%> clay, pH 6.18 in CaCh, 1.15% organic
carbon) was obtained from Stolpe, Germany and characterized by RCC Ltd., Itingen, Switzerland
(p. 15, Appendix II, p. 58). USDA soil texture classification was not specified, but particle size
distributions corresponded to USDA soil particle size distributions.
ILV (MRID 50393501): Mean recoveries and RSDs for GC-MS analysis using the quantitation ion
were within guidelines (mean 70-120%; RSD <20%) for propargite and TBPC at fortification levels
of 0.0100 mg/kg (LOQ) and 0.100 mg/kg (lOxLOQ) in one soil matrix (p. 17, Tables 3-4, pp. 23-
24). Analytes were identified using three ions, but recovery results were only reported for the
quantitation ion. The loamy sand soil (PD-SOIL-PF-O-6"; 80% sand, 14% silt, and 6% clay, pH 6.2
in 1:1 soil: water ratio, 0.88% organic matter Walkley-Black) was obtained from North Dakota and
characterized by Agvise Laboratories, Northwood, North Dakota (USDA soil texture classification;
p. 12, Appendix II, p. 48). The number of trials in the ILV was not specified, but the reviewer
assumed that the method was validated in the first trial based on communications between the ILV
and the Study Sponsor (pp. 10, 14-15; Appendix I, p. 41; Appendix IV, p. 56). The ECM was
performed by the ILV with only insignificant modifications to the analytical equipment and the
identification of two critical steps (pp. 14-15; Tables 1-2, pp. 20-22, Appendix IV, p. 55). The
reviewer noted that the ILV substituted glass centrifuge tubes and glass pipettes for plastic, but this
appeared to be a lab equipment preference instead of a required ILV modification.
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
Table 2. Initial Validation Method Recoveries for Propargite and TBPC in Soil
Analyte
Fortification
Number
Recovery
Mean
Standard
Relative
Standard
Deviation (%)
Level (mg/kg)
of Tests
Range (%)
Recovery (%)
Deviation (%)
Sandy Loam Soil1
Quantitation ion2
Propargite
0.01 (LOQ)
5
79.1-102
92.9
9.90
10.7
0.10
5
92.2-98.9
96.3
2.48
2.57
TBPC
0.01 (LOQ)
5
97.6-119
107
8.07
7.54
0.10
5
89.1-99.8
94.1
4.27
4.54
Data (uncorrected recovery results, pp. 20-23) were obtained from Tables I-IV, pp. 29-32; Appendix III, pp. 61-64 of
MRID 50593501.
1 The sandy loam soil (Batch July-01; 77.25% sand, 13.41% silt, and 9.34% clay, pH 6.18 in CaCk 1.15% organic
carbon) was obtained from Stolpe, Germany and was characterized by RCC Ltd., Itingen, Switzerland (p. 15,
Appendix II, p. 58). USDA soil texture classification was not specified, but particle size distributions corresponded to
USD A soil particle size distributions.
2 Propargite was identified using three ions; one for quantitation (Q) and two for confirmation (C): m/z 350 (Q), m/z
173 (CI), and m/z 150 (C2); TBPC was identified using three ions; m/z 248 (Q), m/z 150 (CI), and m/z 233 (C2) (pp.
15, 20 of MRID 50593501). The ECM provided recovery values for the quantitation ion but did not provide recovery
values for the two confirmation ions.
Table 3. Independent Validation Method Recoveries for Propargite and TBPC in Soil
Analyte
Fortification
Number
Recovery
Mean
Standard
Relative
Standard
Deviation (%)
Level (mg/kg)
of Tests
Range (%)
Recovery (%)
Deviation (%)
Loamy Sand Soil1
Quantitation ion2
Propargite
0.0100 (LOQ)
5
66.9-105
85.1
16.6
19.5
0.100
5
75.5-103
82.5
11.6
14.0
TBPC
0.01 (LOQ)
5
85.7-95.3
90.1
4.44
4.93
0.10
5
86.7-91.3
89.2
1.70
1.90
Data (uncorrected recovery results, pp. 15-16) were obtained from p. 17, Tables 3-4, pp. 23-24 of MRID 50393501).
1 The loamy sand soil (PD-SOIL-PF-O-6"; 80% sand, 14% silt, and 6% clay, pH 6.2 in 1:1 soil:water ratio, 0.88%
organic matter Walkley-Black) was obtained from North Dakota and characterized by Agvise Laboratories,
Northwood, North Dakota (USDA soil texture classification; p. 12, Appendix II, p. 48).
2 Propargite was identified using the primary ion for quantitation ion of propargite of m/z 350, and TBPC was identified
using the primary ion for quantitation of TBPC of m/z 248 (pp. 15, 20 of MRID 50593501). Quantitation was
performed using the primary quantitation ion only. Quantitation was not performed using the response of the two
confirmation ions, and as a result, the ILV did not provide recovery values for the two confirmation ions.
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
III. Method Characteristics
In the ECM, the Limit of Quantification (LOQ) was set at 0.01 mg/kg for propargite and TBPC in
soil (p. 26, Appendix IV, p. 70 of MRID 50593501). The LOQ was reported from the ECM in the
ILV (p. 13 of MRID 50393501). No calculation was provided for the method LOQ in the ECM or
ILV. In the ECM, the Limit of Detection (LOD) for propargite and TBPC was estimated as at least
one-half or less of the response of the lowest calibration standard, 0.05 |ig/mL, according to:
0.05 |ig (STD) / 10 g = 0.005 mg/kg
The ECM stated the validity of the LOD must be demonstrated experimentally; the hexane extract
of a control sample would be fortified at the level above, and the chromatogram must show that the
peak is clearly identifiable (Appendix IV, p. 90 of MRID 50593501). Chromatograms for the lowest
calibration standard, 0.05 |ig/mL, for propargite and TBPC were provided (Figure 7, p. 40, Figure
10, p. 43 of MRID 50593501), and the ECM reported the LOD as 0.005 mg/kg (p. 26 of MRID
50593501). In the ILV, the LOD for propargite and TBPC were 0.00500 mg/kg and were calculated
as the product of the lowest calibration standard (0.0500 mg/L) and the dilution factor of the matrix
blank sample (0.100; p. 14 of MRID 50393501).
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
Table 4. Method Characteristics for Propargite and TBPC in Soil
Propargite
TBPC
Limit of
Quantitation (LOQ)
ECM
0.01 mg/kg
0.01 mg/kg
ILV
Limit of Detection
(LOD)
ECM
0.005 mg/kg
0.005 mg/kg
ILV
Linearity
(calibration curve r2
and concentration
range)
ECM1
r2 = 0.993317966 (LOQ)
r2 = 0.995346457 (lOxLOQ)
r2 = 0.964808136 (LOQ)
r2 = 0.997234486 (lOxLOQ)
ILV
r2 = 0.9960
r2 = 0.9898
Concentration range
0.05-0.2 ng/mL
Repeatable
ECM2-3
Yes at LOQ and lOxLOQ.
ILV4-5
Yes at LOQ and lOxLOQ.
Reproducible
Yes at LOQ and lOxLOQ.
Specific
ECM
Yes, matrix interferences were
<30% of the LOQ (based on peak
area).6
Yes, no peaks were detected
in the controls.
ILV
Yes, no peaks were detected at the analytes' retention times
in the controls.
ECM/ILV
Some minor baseline interference was observed in the confirmation
ion chromatograms.7
Data were obtained from Appendix III, pp. 61-64 (calibration coefficients); Tables I-IV, pp. 29-32, Appendix III,
pp. 61-64 (recovery results); pp. 21, 26, Figures 1-4, pp. 34-37, Figures 7-18, pp. 40-51 (chromatograms) of MRID
50593501; p. 16, Figures 1 and 7, pp. 25, 31 (calibrationcoefficients); p. 17, Tables 3-4, pp. 23-24 (recovery results);
Figures 1 and 7, pp. 25, 31 (calibration curves); Figures 2-6, pp. 26-30, Figures 8-12, pp. 32-36 (chromatograms) of
MRID 50393501. All results reported for Q ions unless otherwise noted.
1 In the ECM, two coefficients of determination (r2) values were provided for propargite and TBPC because the LOQ
and lOxLOQ were run as separate batches (Appendix III, pp. 61-64 of MRID 50593501). The calibration curve
reported for the propargite lOxLOQ set was the second attempt. The r2 values for propargite and TBPC presented in
Figures 5 and 6 of the ECM were not included in this table because these curves demonstrated detector response
using the ratio of the responses of the calibration standards and calibration internal standards (pp. 17, 24, Figures 5-6,
pp. 38-39 of MRID 50593501).
2 In the ECM, the sandy loam soil (Batch July-01; 77.25% sand, 13.41% silt, and 9.34% clay, pH 6.18 in CaCk 1.15%
organic carbon) was obtained from Stolpe, Germany and characterized by RCC Ltd., Itingen, Switzerland, (p. 15,
Appendix II, pp. 57-58). USDA soil texture classification was not specified, but particle size distributions
corresponded to USDA soil particle size distributions.
3 In the first set of ECM lOxLOQ samples, two out of five recoveries for propargite were greater than 110%; as a result,
the analysis was repeated; the high recoveries were attributed to an error in spiking of the two samples. Data for the
second attempt at lOxLOQ was reported (p. 25, Table II, p. 30, Appendix III, p. 62 of MRID 50593501).
4 In the ILV, the loamy sand soil (PD-SOIL-PF-O-6"; 80% sand, 14% silt, and 6% clay, pH 6.2 in 1:1 soil:water ratio,
0.88% organic matter Walkley-Black) was obtained from North Dakota and characterized by Agvise Laboratories,
Northwood, North Dakota (USDA soil texture classification; p. 12, Appendix II, p. 48 55 of MRID 50393501).
5 The number of trials in the ILV was not specified, but the reviewer assumed that the method was validated in the first
trial based on communications between the ILV and the Study Sponsor (pp. 10, 14-15; Appendix I, p. 41; Appendix
IV, p. 56 55 of MRID 50393501). The ILV validated the ECM with only insignificant modifications to the analytical
equipment and the identification of two critical steps (pp. 14-15; Tables 1-2, pp. 20-22, Appendix IV, p. 55). The
reviewer noted that the ILV substituted glass centrifuge tubes and glass pipettes for plastic, but this appeared to be a
lab equipment preference instead of a required ILV modification.
6 In the ECM, three control samples for propargite at the LOQ were analyzed. There was no response in two of the
control samples; one control showed a response of ca. 30% of the LOQ based on peak area and was footnoted as an
"artifact" (Appendix III, p. 61 of MRID 50593501). The chromatogram of this control was not provided for review.
7 A confirmatory method is not typically required where GC/MS methods are used as the primary method(s) to generate
study data. Minor baseline interference was observed in the ECM and ILV confirmation ion chromatograms for the
controls for propargite and TBPC at the LOQ (Figure 13, p. 46 and, Figure 16, p. 49 of MRID 50593501; Figure 4, p.
28, and Figure 10, p. 34 of MRID 50393501).
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
IV. Method Deficiencies and Reviewer's Comments
1. For quantitation analysis, ECM linearity was not satisfactory for propargite analysis in sandy
loam soil, r2 = 0.993317966 (LOQ) (Appendix III, p. 61 of MRID 50593501), and TBPC in
sandy loam soil, r2 = 0.964808136 (LOQ) (Appendix III, p. 63 of MRID 50593501).
For quantitation analysis, ILV linearity was not satisfactory for TBPC analysis in loamy sand
soil, r2 = 0.9898 (p. 41, Figure 7, p. 31 of MRID 50393501).
Linearity is satisfactory when r2 >0.995.
2. The OCSPP 850.6100 guidance suggests for a given sample matrix, the registrant should select
the most difficult analytical sample condition from the study (e.g., high organic content versus
low organic content in a soil matrix) to analyze from the study to demonstrate how well the
method performs. It could not be determined that the ILV were provided with the most difficult
matrix with which to validate the method since only one soil matrix was tested. The ECM tested
one sandy loam soil matrix having 1.15% organic carbon, and the ILV tested one loamy sand
soil matrix having 0.88% organic matter (p. 15, Appendix II, p. 58 of MRID 50593501; p. 12,
Appendix II, p. 48 of MRID 50393501). Additionally, since no terrestrial field dissipation
studies were submitted, it not be determined if the ILV soil matrix covered the range of soils
used in the terrestrial field dissipation studies. Even though a certain number of soil matrices is
not specified in the OCSPP guidelines, more than one soil matrix would need to be included in
an ILV in order to cover the range of soils used in the terrestrial field dissipation studies.
Additionally, the ECM soil matrix characterization was not specified as USD A soil texture
classification, but particle size distributions corresponded to USDA soil particle size
distributions (p. 15, Appendix II, p. 58 of MRID 50593501).
3. The number of trials required by the ILV to validate the ECM was not reported in the ILV. The
reviewer assumed that the method was validated in the first trial based on communications
between the ILV and the Study Sponsor (pp. 10, 14-15; Appendix IV, p. 56 of MRID
50393501). The reviewer also noted that the ILV protocol stated that the Sponsor was to be
informed if any of the trials was unsuccessful before additional attempts are made (Appendix I,
p. 41). No communication of failed trials occurred between the ILV and the Study Sponsor
(Appendix IV, p. 56).
4. In the ECM, three control samples for propargite at the LOQ were analyzed (Appendix III, p. 61
of MRID 50593501). There was no response in two of the control samples; however, one
control showed a response of ca. 30% of the LOQ (based on peak area) and was footnoted as an
"artifact". The "artifact" was quantified as
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
be the same as specified in the ECM method (p. 14; Table 1, p. 20, Appendix IV, p. 55 of MRID
50393501). The reviewer noted that the ILV substituted glass centrifuge tubes and glass pipettes
for plastic, but this appeared to be a lab equipment preference instead of a required ILV
modification.
6. For the ECM method, acetonitrile was specified for rinsing the 50 mL centrifuge tubes after
evaporation on the N-EVAP on p. 19 of MRID 50593501; however, the procedures in Appendix
IV, p. 85 of MRID 50593501 specifies hexane for the rinse. The ILV used acetonitrile (Table 1,
p. 20 of MRID 50393501).
7. In the ECM, propargite and TBPC were quantified using the peak areas ratio of the m/z 350 ion
in the sample or fortified control to that of internal standard, m/z 350 sPi /173 istd (Ratio sPi; pp.
20-22 of MRID 50593501). The amount (|ig) of analyte was determined by using Ratio sPi in the
linear regression equation. The concentration was determined using the sample weight. In the
ILV, propargite and TBPC were quantified using the response of the primary quantitation ion
only (m/z 350 for propargite and m/z 248 for TBPC; pp. 15-16 of MRID 50393501). The
concentration was determined using the linear regression equation.
8. The ECM did not provide the recovery values for the confirmation ions for propargite or TBPC,
and the ILV did not report the response or recovery values for the confirmation ions for
propargite or TBPC. In the case of the confirmation analyses, the reviewer did not consider this
guideline deviation to be significant since a confirmatory method is not typically required where
GC/MS methods are used as the primary method(s) to generate study data
9. Communications were documented on an Arysta LifeScience ILV Assessment Form (Appendix
IV, p. 56 of MRID 50393501). All communications were between ILV EAG Laboratories and
the sponsor Arysta LifeScience and involved completion and approval of independent
validation.
10. In the ECM, the Limit of Quantification (LOQ) was set at 0.01 mg/kg for propargite and TBPC
in soil. The LOQ was reported from the ECM in the ILV. No calculation was provided for the
method LOQ in the ECM or ILV. In the ECM, the Limit of Detection (LOD) for propargite and
TBPC was estimated as at least one-half or less of the response of the lowest calibration
standard, 0.05 |ig/mL, according to: 0.05 |ig (STD) / 10 g = 0.005 mg/kg. In the ILV, the LOD
for propargite and TBPC was 0.00500 mg/kg and were calculated as the product of the lowest
calibration standard (0.0500 mg/L) and the dilution factor of the matrix blank sample (0.100).
The reported limit of quantitation (LOQ) was set as the lowest level of method validation
(LLMV). Further work could have been done to explore the actual LOQ. This means that
concentrations can be reliably quantified at the LOQ (i.e., LLMV), but whether lower
concentrations may also be reliably quantified is uncertain.
11. In the ECM, the time required to complete the preparation of one set of samples for GC-MSD
was reported as one working day (8 hours), followed by ca. 11 hours for GC/MSD analysis
(unattended), and then ca. 4 hours of data processing for one chemist totalling 12 person-hours
(p. 27 of MRID 50593501). In the ILV, one analyst-day (ca. 8 person-hours) was required to
prepare stocks and solution, an additional ca. 10 person-hours were required to process and
extract each set of samples, GC/MS analysis time was ca. 20 instrument-hours, and data
processing time of one MS transition for quantitation and confirmation analyses (ca. 2 person-
Page 9 of 11
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
hours), totaling 4 days (ca. 20 person-hours and ca. 20 instrument-hours; Appendix IV, pp. 55-
56 of MRID 50393501).
V. References
U.S. Environmental Protection Agency. 2012. Ecological Effects Test Guidelines, OCSPP
850.6100, Environmental Chemistry Methods and Associated Independent Laboratory
Validation. Office of Chemical Safety and Pollution Prevention, Washington, DC. EPA 712-
C-001.
U.S. Environmental Protection Agency. 2014 Propargite: Problem Formulation for Environmental
Fate, Ecological Risk, Endangered Species, and Drinking Water Exposure Assessments in
Support of Registration Review. Office of Pesticide Programs, Environmental Fate and
Effects Division. DP 416479.
40 CFR Part 136. Appendix B. Definition and Procedure for the Determination of the Method
Detection Limit-Revision 1.11, pp. 317-319.
Page 10 of 11
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Propargite (PC 097601)
MRIDs 50593501 / 50393501
Attachment 1: Chemical Names and Structures
Propargite
IUPAC Name:
CAS Name:
CAS Number:
SMILES String:
(1RS,2RS; lRS,2SR)-2-(4-tert-butylphenoxy)cyclohexyl prop-2-ynyl
sulfite
2-[4-(l, 1-dimethylethyl)phenoxy]cyclohexyl 2-propyn-l-yl sulfite
2312-35-8
CC(C)(C)c2ccc(OC 1CCCCC10S(=0)0CC#C)cc2
TBPC
IUPAC Name:
CAS Name:
CAS Number:
SMILES String:
Q-~-Q-tr
OH
Page 11 of 11
2-(4-(T ert-butyl)phenoxy)cyclohexan-1 -ol
Not reported
1942-71-8
OC1 CCCCC 1 OC2=CC=C(C(C)(C)C)C=C2
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