Chloropicrin (PC 081501) MRIDs 49831301/50030701
Analytical method for chloropicrin in air from air sampling tubes
Reports: ECM: EPAMRID No.: 49831301. Arndt, T., and C. Warling. 2016. Method
Validation of an Analytical Method for Monitoring Chloropicrin in Air.
PTRL Project No.: 2540W. Report prepared by PTRL West (a division of
EAG Laboratories), Hercules, California, and sponsored and submitted by
Chloropicrin Manufacturers' Task Force, Mojave, California, and
Toxicology Consultants, Inc., Gibsonia, Pennsylvania; 92 pages. Final report
issued February 17, 2015; Amended Study dated January 22, 2016.
Document No.
Guideline:
Statements:
Classification:
PC Code:
ILV: EPA MRID No. 50030701. Bendig, P., and C. Wabbel. 2016.
Independent Laboratory Validation (ILV) of an Analytical Method for
Monitoring Chloropicrin in Air. PTRL Europe ID: P 3822 G. Report
prepared by PTRL Europe, Ulm, Germany, sponsored and submitted by
Chloropicrin Manufacturers' Task Force, Mojave, California; 42 pages.
Final report issued September 8, 2016.
MRIDs 49831301 & 50030701
850.6100
ECM: The study was conducted in accordance with USEPA FIFRA Good
Laboratory Practice (GLP) standards (40 CFR, Part 160 p. 3 of MRID
49831301). Signed and dated No Data Confidentiality, GLP, and Quality
Assurance statements were provided (pp. 2-4). A statement of authenticity
was included with the QA statement.
ILV: The study was conducted in accordance with German GLP standards,
which are based on OECD GLP standards, which are accepted by European
communities, the USA (FDA and EPA, FIFRA GLP standards, 40 CFR, Part
160) and Japan (p. 3; Appendix 1, p. 40 of MRID 50030701). Signed and
dated No Data Confidentiality, GLP, Quality Assurance, and Authenticity
statements were provided (pp. 2-5; Appendix 1, p. 40).
This analytical method is classified as acceptable. ECM is classified as
supplemental due to the number of samples was insufficient at all
fortification levels (less than five as required). However, the deficiency has
been made up in ILV, which has used five samples for each replicate.
081501
EFED Final
Reviewer:
CDM/CSS-
Dynamac JV
Reviewers:
James Lin
Environmental Engineer
LisaMuto, M.S.
Environmental Scientist
Joan Gaidos, Ph.D.,
Environmental Scientist
Signature:
Date: 12/13/2018
Signature:
Date:
Signature:
Date:
08/17/2018
09/14/2018
Page 1 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
This Data Evaluation Record may have been altered by the Environmental Fate and Effects
Division subsequent to signing by CDM/CSS-Dynamac JVpersonnel. The CDM/CSS-Dynamac
Joint Venture role does not include establishing Agency policies.
Executive Summary
The analytical method, PTRL West Project No. 2540W, is designed for the quantitative
determination of chloropicrin in air from from air sampling tubes at the LOQ of 30.0 ng/air
sample cartridge using GC/MS/MS. The LOQ is less than the lowest toxicological level of
concern in air. The ECM and ILV test matrices were XAD-4 resin air sampling cartridges. Air
was drawn through the air sampling apparatuses at ca. 100 mL/min., ca. 40% relative humidity,
and 20-25°C for 48 hours before extraction. Although the specific number of trials was not
reported in the ILV, the reviewer assumed that method was validated in the first trial with
insignificant modifications of the analytical instrumentation. All ILV and ECM data regarding
repeatability, accuracy, precision, linearity, and specificity were satisfactory for chloropicrin,
except that the number of samples was insufficient at all fortification levels in the ECM.
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
Chloropicrin
49831301
50030701
Air1-2
17/02/2015
(Final)
22/01/2016
(Amended)
Chloropicrin
Manufacturers'
Task Force
GC/MS/MS
30 ng/tube
1 In the EM, the air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10
mm O.D. x 156 mm L) air sampling tubes (SKC Inc. Cat No. 092314-002) attached to the manifold ports with
Tygon® tubing to a SKC 224-44XR or SKC 224-PPCXR4 sample pump (pp. 14-15, 18-19; Table 1, p. 33; Figure
1, p. 38 of MRID 49831301). After chloropicrin was introduced, air was drawn through the air sampling
apparatuses at ca. 100 mL/min., 38.2-40.1% relative humidity, and 20.4-21.9°C for 48 hours before extraction.
2 In the ILV, the air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10
mm O.D. x 156 mm L) air sampling tubes (pp. 12, 14-15, 17; Figure 1, p. 26; Appendix 3, p. 42 of MRID
50030701). After chloropicrin was introduced, air was drawn through the air sampling apparatuses at ca. 100
mL/min., 42-51% relative humidity, and ca. 25°C for 48 hours before extraction.
Page 2 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
I. Principle of the Method
The air sampling apparatus was composed of a foil-wrapped XAD-4 resin (1400/250 mg; 10 mm
O.D. x 156 mm L) air sampling tubes (SKC Inc. Cat No. 092314-002) attached to the manifold
ports with Tygon® tubing to a SKC 224-44XR or SKC 224-PPCXR4 sample pump (pp. 14-15,
18-19; Figure 1, p. 38 of MRID 49831301). The air sampling apparatuses were set-up with
triplicate tubes for the fortifications and duplicate tubes for the controls. After the airflow of each
sample tube was adjusted to ca. 100 mL/min., the appropriate amount of chloropicrin in ethyl
acetate was introduced to the apparatus, if necessary, via the trapping flask inlet with microliter
syringe. Air was drawn through the air sampling apparatuses for 48 hours before extraction;
temperature, humidity, and air flow was monitored throughout the sampling time. Sample tubes
were extracted on the same day as the end of the trapping period.
For extraction, the front-end glass wool and front-side sorbent beads of the opened sorbent tube
were transferred to chilled 10 mL ethyl acetate in an amber 16-mL vial (p. 21 of MRID
49831301). The back-side sorbent beads of the opened sorbent tube were transferred to chilled 5
mL ethyl acetate in an amber 10-mL vial. After vortexing, the vials were shaken for ca. 1 hour
on a wrist-action shaker. The supernatants were transferred to 8 mL amber storage vials, diluted
with ethyl acetate as necessary (10X for lOxLOQ and 500X for 500>82 and m/z 119—>84. Expected retention time was ca.
6.2 minutes.
The residues in the front and back extracts were quantified separately, then summed (Figure 22,
p. 60 of MRID 49831301).
In the ILV, the ECM was performed as written, except for a different analytical instrumentation
(pp. 12, 14-15, 17; Figure 1, p. 26 of MRID 50030701). A Thermo Trace 1310 GC coupled to a
Thermo TSQ 8000 Evo Triple Quad MS was used. All other GC/MS/MS parameters were the
same as those of the EM. Expected retention time was ca. 5 minutes.
The Limit of Quantification (LOQ) for chloropicrin in air was 30 ng chloropicrin per tube which
was converted based on recorded air flow to 0.105 |ig/m3 in the ECM and ca. 0.1 |ig/m3 in the
ILV (p. 25 of MRID 49831301; p. 11 of MRID 50030701). The Limit of Detection (LOD) was
0.5 ng/mL in the ECM and ILV.
Page 3 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
II. Recovery Findings
EM (MRID 49831301): Mean recoveries and relative standard deviations (RSDs) were within
guideline requirements (mean 70-120%; RSD <20%) for analysis of chloropicrin from air
sampling tubes at fortification levels of 30 ng/tube (0.105 |ig/m3; LOQ), 300 ng/tube (1.00
|ig/m3; lOxLOQ), and 15,000 ng/tube (50.7 |ig/m3; 500>
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
Table 2. Initial Validation Method Recoveries for Chloropicrin in Air1
Fortification
Analyte
Level
Number
Recovery
Mean
Standard
Relative Standard
[ng/tube
(jig/m3)]3
of Tests
Range (%)
Recovery (%)
Deviation (%)4
Deviation (%)
XAD-4 sorbent air sampling tube
Quantitation ion transition
30 (0.105)
3
88-97
94
5
5.3
Chloropicrin
300 (1.00)
3
72-90
81
9
11.1
15,000 (50.7)
3
81-86
83
3
3.2
Confirmation ion transition
30 (0.105)
3
86-93
90
4
3.9
Chloropicrin
300 (1.00)
3
76-91
81
8
10.3
15,000 (50.7)
3
78-83
81
3
3.1
Data (uncorrected recovery results; pp. 23-24) were obtained from Table 2, p. 34 and Table 4, p. 36 of MRID
49831301 and DER Attachment 2.
1 The air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10 mm O.D. x
156 mm L) air sampling tubes (SKC Inc. Cat No. 092314-002) attached to the manifold ports with Tygon® tubing
to a SKC 224-44XR or SKC 224-PPCXR4 sample pump (pp. 14-15, 18-19; Table 1, p. 33; Figure 1, p. 38). After
chloropicrin was introduced, air was drawn through the air sampling apparatuses at ca. 100 mL/min., 38.2-40.1%
relative humidity, and 20.4-21.9°C for 48 hours before extraction; sample tubes were extracted on the same day as
the end of the trapping period.
2 Chloropicrin was identified with the following two ion transitions (primary and confirmation, respectively): m/z
117—>82 and m/z 119—>84.
3 Reported |ig/m3 were calculated in the study report based on measured air flow.
4 Standard deviations were reviewer-calculated using the data in the study report since the study author did not
report these values (see DER Attachment 2). Rules of significant figures were followed.
Page 5 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
Table 3. Independent Validation Method Recoveries for Chloropicrin in Air12
Fortification
Analyte
Level
Number
Recovery
Mean
Standard
Relative Standard
[ng/tube
(jig/m3)]3
of Tests
Range (%)
Recovery (%)
Deviation (%)4
Deviation (%)
XAD-4 sorbent air sampling tube
Quantitation ion transition
30 (0.101)
5s
79-94
88
5
6
Chloropicrin
300 (1.01)
56
77-92
82
6
8
15,000 (50.5)
5s
94-109
99
6
6
Confirmation ion transition
30 (0.101)
5s
81-94
89
5
6
Chloropicrin
300 (1.01)
56
77-97
84
8
9
15,000 (50.5)
5s
96-108
100
5
5
Data (uncorrected recovery results, p. 19) were obtained from Table 1, p. 23 of MRID 50030701.
1 The air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10 mm O.D. x
156 mm L) air sampling tubes (SKC Inc. Cat No. 092314-002) attached to the manifold ports with Tygon® tubing
to a SKC 224-44XR or SKC 224-PPCXR4 sample pump (pp. 12, 14-15, 17; Figure 1, p. 26; Appendix 3, p. 42).
After chloropicrin was introduced, air was drawn through the air sampling apparatuses at ca. 100 mL/min., 42-
51% relative humidity, and ca. 25°C for 48 hours before extraction; sample tubes were extracted on the same day
as the end of the trapping period.
2 Chloropicrin was identified with the following two ion transitions (primary and confirmation, respectively): m/z
117—>82 and m/z 119—>84.
3 Reported |ig/m3 were calculated in the study report based on measured air flow.
4 Standard deviations were reviewer-calculated using the data in the study report since the study author did not
report these values (see DER Attachment 2). Rules of significant figures were followed.
5 The reported value for the first sample was the means of two injections. This was done to demonstrate
repeatability of injection (p. 21).
6 The reported value for the first and last samples was the means of two injections. This was done to demonstrate
repeatability of injection (p. 21).
III. Method Characteristics
The LOQ for chloropicrin in air was 30 ng chloropicrin per tube which was converted based on
recorded air flow to 0.105 |ig/m3 in the ECM and ca. 0.1 |ig/m3 in the ILV (p. 25 of MRID
49831301; p. 11 of MRID 50030701). In the ECM and ILV, the LOQ was determined by the rate
of air flow (ca. 100 mL/min.) when trapping for 48 hours at a 30-ng injection amount. The LOD
was 0.5 ng/mL in the ECM and ILV. In the ECM, the LOD was calculated as 3xs the standard
deviation of the peak area multiplied by the standard concentration (1 ng/mL) divided by the
average peak area. In the ILV, the LOD was determined based on the 10 mL of ethyl acetate
which was used to extract the air sampling samples. No calculations or comparisons to
background levels were reported to justify the LOQ for the method in the ECM or ILV, or the
LOD in the ILV.
Page 6 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
Table 4. Method Characteristics
Analyte1
Chloropicrin
Limit of Quantitation
(LOQ)
ECM
30 ng/tube (0.105 |ig/m3)
ILV
30 ng/tube (ca. 0.10 |ig/m3)
Limit of Detection
(LOD)
ECM
0.05 |ig/m3
ILV
Linearity (calibration
curve r2 and
concentration range)1
ECM
r2 = 0.99711841 (Q)
r2 = 0.99668969 (C)
(0.5-20 ng/mL)
ILV
r2 = 0.9983 (Q)
r2 = 0.9988 (C)
(0.50-30 ng/mL)
Repeatable
ECM2
Yes at LOQ, lOxLOQ and 500/LOQ. but n = 3
(air sampling tubes)
ILV3-4
Yes at LOQ, lOxLOQ and 500xLOQ
(air sampling tubes)
Reproducible
Yes at LOQ, lOxLOQ and 500xLOQ
Specific
ECM
Yes, matrix interferences were ca. 9% of the LOQ (based on peak area).
ILV
Yes, matrix interferences were <3% of the LOQ (based on peak area).
Data were obtained from p. 25 (LOQ/LOD); Table 2, p. 34 and Table 4, p. 36 (recovery data); Figure 2, pp. 39-40
(calibration curve); Figures 3-21, pp. 41-59 (chromatograms) of MRID 49831301; p. 11 (LOQ/LOD); Table 1, p. 23
(recovery data); Figures 2-3, pp. 27-28 (calibration curves); Figures 4-13, pp. 29-38 (chromatograms) of MRID
50030701.
1 Quadratic equations were used in the ECM and ILV.
2 In the EM, the air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10
mm O.D. x 156 mm L) air sampling tubes (SKC Inc. Cat No. 092314-002) attached to the manifold ports with
Tygon® tubing to a SKC 224-44XR or SKC 224-PPCXR4 sample pump (pp. 14-15, 18-19; Table 1, p. 33; Figure
I, p. 38 of MRID 49831301). After chloropicrin was introduced, air was drawn through the air sampling
apparatuses at ca. 100 mL/min., 38.2-40.1% relative humidity, and 20.4-21.9°C for 48 hours before extraction;
sample tubes were extracted on the same day as the end of the trapping period.
3 In the ILV, the air sampling apparatus was composed of triplicate foil-wrapped XAD-4 resin (1400/250 mg; 10
mm O.D. x 156 mm L) air sampling tubes (pp. 12, 14-15, 17; Figure 1, p. 26; Appendix 3, p. 42 of MRID
50030701). After chloropicrin was introduced, air was drawn through the air sampling apparatuses at ca. 100
mL/min., 42-51% relative humidity, and ca. 25°C for 48 hours before extraction; sample tubes were extracted on
the same day as the end of the trapping period.
4 Although the specific number of trials was not reported in the ILV, the reviewer assumed that method was
validated in the first trial with insignificant modifications of the analytical instrumentation (pp. 9-10, 12, 14-15,
20, 22 of MRID 50030701).
5 The reviewer noted that the residues in the back portion extract of the control sample was quantified as 14 ct
(0.175 ng/mL), while the residues in the back portion extract of the LOQ sample was 0 ct (0.142 ng/mL; Figure
II, p. 49; Figure 13, p. 51; Figure 22, p. 60 of MRID 49831301.
IV. Method Deficiencies and Reviewer's Comments
1. Communications between the ECM and ILV were not addressed in the ECM or ILV.
2. In the ECM, the number of samples was insufficient at all fortification levels (n = 3;
Table 2, p. 34 of MRID 49831301; DER Attachment 2). OCSPP guideline state that a
minimum of five spiked replicates were analyzed at each concentration (i.e., minimally,
the LOQ and 10x LOQ) for each analyte.
Page 7 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
3. The number of trials required by the ILV to validate the ECM was not reported. Although
the specific number of trials was not reported in the ILV, the reviewer assumed that
method was validated in the first trial with insignificant modifications of the analytical
instrumentation (pp. 9-10, 12, 14-15, 20, 22 of MRID 50030701).
4. Concurrent recoveries (set forts) were prepared in the ECM to assess extraction
efficiency (p. 28, Table 3, p. 35 of MRID 49831301). Recoveries [mean (RSD)] were
95% (2.8%), 101%) (1.0%), and 91% (1.9%) for the quantitation analysis of the LOQ,
lOxLOQ and 500>
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
11. It was reported for the ILV that one sample set required ca. 48 hours of air sampling, ca.
3 hours for extraction and dilution, and ca. 16 hours of GC/MS/MS analysis (p. 22 of
MRID 50030701). The total time was reported as ca. 3 working days.
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.
40 CFR Part 136. Appendix B. Definition and Procedure for the Determination of the Method
Detection Limit-Revision 1.11, pp. 317-319.
Page 9 of 10
-------
Chloropicrin (PC 081501)
MRIDs 49831301/50030701
Attachment 1: Chemical Names and Structures
Chloropicrin
IUPAC Name:
CAS Name:
CAS Number:
SMILES String:
CI
CI — i —
I
Page 10 of 10
T ri chl oronitrom ethane
Not reported
76-06-2
Not found
------- |