OFFICE OF CHEMICAL SAFETY
AND POLLUTION PREVENTION UNITED STATES ENVIRONMENTAL PROTECTION AGENC Y
WASHINGTON, D.C. 20460



### January 20, 2015

PC Code: 098301

MEMORANDUM DP Barcode: 424560

SUBJECT: Transmittal of a Data Evaluation Record for Analytical Methods for Aldicarb and Two Degradates

FROM: Edmund Wong, Environmental Chemist Greg Orrick, Environmental Scientist (Reviewer)

Environmental Risk Branch 2 Environmental Fate and Effects Division (7507P)

THRU: Brian Anderson, Branch Chief

Environmental Risk Branch 2 Environmental Fate and Effects Division (7507P)

TO: Susan Bartow, Chemical Risk Manager Kevin Costello, Acting Branch Chief Risk Management and Implementation Branch IV Pesticide Re-evaluation Division (7508P)

This memorandum is to inform you that the analytical method for aldicarb, aldicarb sulfone, and aldicarb sulfoxide in water (ECM & ILV) have been reviewed and finalized. Study

MRIDs and classification are listed in Table 1 below.

Table 1. DER for Environmental Fate Studies of Aldicarb & Degradates

MRID Study Type (OCSPP Guideline) DER Electronic File Name(s) Study

Classification

49515901

&

49515902 Environmental Chemistry

Method in Water & Independent Laboratory

Validation (850.6100) 098301_49515901_49515902_DER-Fate_850.6100_1-15-

15.docx Acceptable 

### Anderson, Brian

2015.01.26

11:20:30 -05'00' 2015.01.26

14:26:17 -05'00'Aldicarb (PC 098301 ) MRID 49515901, 49515902



### Analytical method for aldicarb, aldicarb sulfone, and aldicarb sulfoxide in water

Report s : ECM: MRID 49515901

. Bianc a , C . 20 14

. Method Validation of Aldicarb, Aldicarb Sulfone, and Aldicarb Sulfoxide in Three Water Types: Surface Water; Ground Water; and Drinking Water : Final Report. Project Number : AU/2014/03 . Unpublished study prepared by JRF America

. 193p.

ILV: MRID 49515902

. Rutt, D.; Budgeon, A . 20 14 . Independent Laboratory

Validation of JRF America Analytical Method AU

- 269R0 “Analytical Method for Analysis of Aldicarb, Aldicarb Sulfone, and Aldicarb Sulfoxide in Three Water Types: Surface Water, Ground Water, and Drinking Water: Final Report. Projec t Number: AU/2014/09. Unpublished study prepared by JRF America. 169p.

Document No. : MRID s 49515901 & 49515902

Guideline : 850.6100

Statements : The method validations were conducted in compliance with FIFRA GLP or UK GLP standards . S igned and dated No Data Confidentiality Claims , GLP Compliance, Quality Assurance, Certification of Authenticity, and Report Approval statements were provided for the ECM and ILV reports

. Classification : This analytical method is classified as acceptable

. It was independently validated upon the first attempt

. PC Code: 098301
Primary

Reviewer: Edmund Wong Signature:

Environmental Chemist Date: Jan

. 13 201 5
Secondary

Reviewer: Gregory Orrick Signature:

Environmental Scientist Date: Jan

. 13 , 201 5

Executive Summary

This analytical method, AU

- 269R0

, is designed for the quantitative determination of aldicarb, aldicarb sulfone, and aldicarb sulfoxide in three water types: surface water, ground water, and drinking water using LC

- MS/MS (see Table 1)

. The method is quantitative for the analytes at the

st ated LOQ of 0. 1 μg/ L

. The ILV was performed in the same laboratory facility that the method was developed ; however, the study d irector, analysts, instruments, and chemicals were distinct

from those of the initial validation

. The independent laboratory was successful at validating the

method. Although several ECM LOD and LOQ recoveries for Aldicarb Sulfone and Aldicarb Sulfoxide were either at baseline noise level or 2x the value, all mean recoveries were within the acceptable range of 70

- 110% and RSD ≤20% for LOQ and 10xLOQ in the primary and confirmatory analys e s. The method is repeat able and reproducible.

Table 1. Analytical Method Summary

Analyte(s) by

Pesticide MRID

EPA

Review Matrix Method

Date Registrant Analysis Limit of Quantitation (LOQ) Environmental Chemistry

Method Independent Laboratory

Validation
Aldicarb, Aldicarb Sulfone, & Aldicarb

Sulfoxide 49515901 49515902

- Water 10/15/14 AgLogic

LLC LC

MS/MS 0. 1 μg / L



### 1Aldicarb (PC 098301 ) MRID 49515901, 49515902



### I. Principle of the Method

Fortified surface, ground or drinking water samples (10 mL ) were vortexed

, centrifuged and then analysed by LC

- MS/MS in positive ion mode

. The method quantifies residues of a ldicarb,

a ldicarb s ulfone, and a ldicarb s ulfoxide in water at the stated LOQ of 0. 1 μg/ L , 10xLOQ of 1.0 μg/ L, and LOD of 0.05 μg/ L

. Each analyte were determined in surface, ground, and drinking water with primary and confirmatory analys e s.

The ILV was performed in the same laboratory facility that the method was developed. To ensure impa rtiality and independence, the s tudy d irector, analysts, instruments, chemicals, analytical standards, etc. were “ distinct and operated separately and without collusion for the validation portion. ” The study d irector and analysts had no prior experience using the method. One attempt per matrix was performed during the course of the ILV.

II. Recovery Findings

Initial Validation Method Recoveries for Analytes in Surface , Ground, and Drinking

Water Primary analysis m ean recoveries and relative standard deviations (RSD) were within guideline requir ements ( a ldicarb mean 102

- 1 05 %, RSD ≤20% ; a ldicarb s ulfone mean 101

- 1 0 9 %, RSD
≤20% ; a ldicarb s ulfoxide mean 103

- 107%, RSD ≤20% ) for LOQ and 10xLOQ samples

. Meanwhile, confirmatory mean recoveries of LOQ and 10x LOQ were 102

- 1 05 % for a ldicarb,

97

- 1 0 7 % for a ldicarb s ulfone, and 102

- 106% for a ldicarb s ulfoxide

. RSD of all analytes in confirmatory analysis were ≤20%

.

Table 2

. Initial Validation M ethod Recoveries for Analytes in Surface Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 7 93.4

- 110 102 5.9 5.7

1 μg/L 5 101

- 108 104 2.6 2.5 Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 7 94

- 110 102 7.1 7.0

1 μg/L 5 101

- 107 102.6 2.5 2.4

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 7 81.5

- 115 103 11.3 11

1 μg/L 5 104

- 118 108.8 5.4 5.0
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 7 89.6

- 116 105 9.0 8.6

1 μg/L 5 104

- 109 106.6 1.8 1.7

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 7 91.7

- 117 104 9.2 8.9

1 μg/L 5 105

- 110 107 2.0 1.9
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 7 85

- 117 102 10.7 10.5

1 μg/L 5 104

- 110 106.2 2.3 2.1



### 2Aldicarb (PC 098301 ) MRID 49515901, 49515902



### Table 3

. Initial Validation M ethod Recoveries for Analytes in Ground Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 7 102

- 109 105 2.5 2.4

1 μg/L 5 103

- 105 104 0.8 0.8
Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 7 101

- 110 104 3.2 3.1

1 μg/L 5 101

- 105 103 1.5 1.4

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 7 101

- 112 107 3.4 3.2

1 μg/L 5 104

- 110 107 2.6 2.4
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 7 87.9

- 107 98 7.9 8.0

1 μg/L 5 105

- 108 106 1.1 1.1

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 7 101

- 110 105 3.3 3.2

1 μg/L 5 101

- 106 103 2.3 2.2
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 7 90.4

- 109 102 7.0 6.9

1 μg/L 5 100

- 109 104 3.7 3.6



### Table 4

. Initial Validation M ethod Recoveries for Analytes in Drinking Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 7 101

- 108 104 2.6 2.5

1 μg/L 5 101

- 109 105 2.9 2.8
Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 7 102

- 109 105 2.4 2.2

1 μg/L 5 100

- 106 103 2.6 2.5

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 7 93

- 112 101 6.0 6.0

1 μg/L 5 98.6

- 108 102 3.5 3.4
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 7 85.3

- 108 97 7.9 8.2

1 μg/L 5 102

- 109 106 2.9 2.7

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 7 97.8

- 112 106 4.4 4.2

1 μg/L 5 101

- 107 104 2.3 2.2
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 7 97.8

- 113 106 5.4 5.1

1 μg/L 5 102

- 110 106 3.3 3.1



### 3Aldicarb (PC 098301 ) MRID 49515901, 49515902



### Independent Validation Method Recoveries for Analytes in Surface , Ground, and Drinking

Water Primary analysis m ean recoveries and relative standard deviations (RSD) were within guideline requirements ( a ldicarb mean 100

- 106%, RSD ≤20%; a ldicarb s ulfone mean 93.4

- 106%, RSD
≤20% ; a ldicarb s ulfoxide mean 93.5

- 106%, RSD ≤20% ) for LOQ and 10xLOQ samples. Meanwhile, confirmatory mean recoveries of LOQ and 10x LOQ were 100

- 106% for a ldicarb,

89.4

- 107 % for a ldicarb s ulfone, and 91

- 101% for a ldicarb s ulfoxide. RSD of all analytes in confirmatory analysis were ≤20%

.

Table 5

. Independent Validation Method Recoveries for Analytes in Surface Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 5 85.2

- 110 101 10.5 10.3

1 μg/L 5 92.6

- 107 102 5.8 5.7
Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 5 78.4

- 110 100 12.5 12.5

1 μg/L 5 86.8

- 113 103 10.2 9.9

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 5 72.5

- 104 93.4 12.5 13.4

1 μg/L 5 89.7

- 103 95.9 5.0 5.2
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 5 82.6

- 95.9 89.4 5.3 5.9

1 μg/L 5 88.2

- 104 93.7 6.2 6.7

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 5 92.8

- 103 96.7 4.1 4.2

1 μg/L 5 86.2

- 97.9 93.5 4.5 4.9
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 5 88.6

- 101 96.9 5.5 5.7

1 μg/L 5 87.1

- 109 101 8.6 8.5



### Table 6

. Independent Validation Method Recoveries for Analytes in Ground Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 5 89.1

- 110 101 8.0 7.9

1 μg/L 5 89.7

- 112 100 8.9 8.9 Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 5 97.7

- 110 103 6.2 6.0

1 μg/L 5 96.1

- 113 106 6.3 5.9

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 5 99.4

- 110 105 4.3 4.1

1 μg/L 5 89

- 104 98.1 6.2 6.3
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 5 103

- 110 107 3.1 2.9

1 μg/L 5 98.4

- 109 105 3.9 3.7



### 4Aldicarb (PC 098301 ) MRID 49515901, 49515902

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 5 93.9

- 107 98.3 5.2 5.3

1 μg/L 5 93.2

- 109 100 5.8 5.8
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 5 72.9

- 107 92.6 13.4 14.5

1 μg/L 5 77.3

- 110 91.9 12.2 13.3



### Table 7

. Independent Validation Method Recoveries for Analytes in Drinking Water

Analyte Fortification

Level (units) Number

of Tests Recovery Range (%) Mean Recovery (%) Standard Deviation (%) Relative Standard

Deviation (%)

Aldicarb Primary Transition (m/z 208 → 88.6)
0.1 μg/L 5 98

- 110 106 5.2 4.9

1 μg/L 5 90.7

- 110 102 7.6 7.4
Confirmatory Transition (m/z 208 → 115.7)
0.1 μg/L 5 92.6

- 110 106 8.4 8.0

1 μg/L 5 9.31

- 107 100 5.8 5.8

Aldicarb Sulfone Primary Transition (m/z 2 40 → 75.5 )
0.1 μg/L 5 100

- 109 106 6.7 6.3

1 μg/L 5 95.4

- 110 103 6.9 6.7
Confirmatory Transition (m/z 240 → 86 )
0.1 μg/L 5 97.6

- 108 104 3.9 3.8

1 μg/L 5 99.4

- 110 100 6.7 6.7

Aldicarb Sulfoxide Primary Transition (m/z 207 → 88.5 )
0.1 μg/L 5 95.1

- 111 106 6.7 6.3

1 μg/L 5 96.2

- 103 102 5.0 4.9
Confirmatory Transition (m/z 207 → 68.5 )
0.1 μg/L 5 83

- 103 91 7.5 8.2

1 μg/L 5 88.2

- 113 98.9 11.1 11.2



### III. Method Characteristics

5Aldicarb (PC 098301 ) MRID 49515901, 49515902



### The LOD was considered to be a concentration equivalent to 50% of the stated LOQ (0.1 μg/ L)

, which i s 0.05 μg/ L for a ldicarb, a ldicarb s ulfone, and a ldicarb s ulfoxide . In some cases, the

LOD was lowered to 24 % of the LOQ (0.0 24 μg/ L) dependent upon the sensitivity, linear range, and conditions of the LC/MS/MS system. The stated LOQ was determined as the lowest

fortification concentration with adequate accuracy (mean recoveries within 70

- 120%) and precision (RSDs ≤20%)

.

The LOD and LOQ values w ere >10x the baseline noise in the control samples for aldicarb in surface, ground, and drinking water

. However , the LOD was < 1 x the baseline noise in drinking water sample s for aldicarb sulfone

. The LOQ was about 2x baseline noise for surface, ground and drinking water for aldicarb sulfone

. For aldicarb sulfoxide, t he LOD was 2x the baseline noise in drinking water sample s, while the LOQ was >4x baseline noise for surface, ground

, and drinking water

.

The method was reproducible for all analytes in surface, ground, and drinking water at the stated LOQ of 0. 1 μg/ L

.

Table 4 . Method Characteristics

Aldicarb Aldicarb Sulfone Aldicarb Sulfoxide
Limit of Quantitation (LOQ) 0. 1 μg/ L 0. 1 μg/ L 0. 1 μg/ L

Limit of Detection (LOD) 0. 05 μg/ L 0.05 μg/L 0.05 μg/L
Linearity (calibration curve r 2 and concentration range) r 2 = 0.99 5 (0. 05

– 1

. 0 μg/L ) r 2 = 0.99 5 (0. 05

– 1

. 0 μg/L) r 2 = 0

. 995 (0. 05

– 1

. 0 μg/L)
Repeatable Yes (RSD <20%) Yes (RSD <20%) Yes (RSD <20%)
Reproducible Yes Yes Yes
Specific Yes Yes Yes



### IV. Method Deficiencies and Reviewer’s Comments

In the ECM, for aldicarb sulfone, t he LOD was at the baseline noise level in drinking water sample s, while the LOQ was about 2x baseline noise for surface, ground and drinking water. For aldicarb sulfoxide, t he LOD was calculated as 2x the baselin e noise in drinking water sample s

. However, mean recoveries for all analytes ( a ldicarb, a ldicarb s ulfone, and a ldicarb s ulfoxide)

we re within the acce ptable range of 70

- 120% and RSD ≤20% in surfa ce, ground, and drinking

water.

No other major deficiencies with the method were found

.

6Aldicarb (PC 098301 ) MRID 49515901, 49515902



### Attachment 1: Chemical Names and Structures

Table 1. Aldicarb, Aldicarb Sulfone, and Aldicarb Sulfoxide

. A

Code Name/ Synonym Chemical Name Chemical Structure

Aldicarb IUPAC: 2

- methyl

- 2(methylthio)propionaldehyde O

- (methylcarbamoyl)oxime

CAS No.: 116

- 06

- 3

Formula: C 7 H 14 N 2 O 2 S

MW: 190

. 26 g/mol

SMILES: C(C)(C)(C=NOC(=O)NC)SC

Aldicarb Sulfone IUPAC: [(E)

- (2

- methyl

- 2

- methylsulfonylpropylidene)amino] N

- methylcarbamate

CAS No.: 1646

- 88

- 4

Formula: C 7 H 14 N 2 O 4 S

MW: 222.26 g/mol

SMILES: CC(C)(/C=N/OC(=O)NC)S(=O)(=O)C

Aldicarb Sulfoxide IUPAC: (E)

- (2

- methanesulfinyl

- 2

- methylpropylidene)amino N

- methylcarbamate

CAS No. : 1646

- 87

- 3

Formula: C 7 H 14 N 2 O 3 S

MW: 206.263 g/mol

SMILES: CNC(=O)O \ N=C \ C(C)(C)S(C)=O

A MW means “molecular weight”. 

### C CH 3



### S CH 3



### CH 3 

### N O O

N

H H 3 

### C

H



### 7