### UN ITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON , D.C. 20460

M E MORANDUM 1 8-FEB

- 20 1 6 O FF I CE O F C llEJ\J I CA L SAF ET Y**A~ D**  POLLITTION PRE VENT IO N

SUBJECT: A ldi carb. R ev iew of R es idu e C he mi s try Dat a Submitted in Res pon se to a Generic Data Call -Jn (GDC I). P

C Code: 098301 Decis i o n No
. : 498310 P

eti ti on N o .: NA Asses s ment Type: NA TXR No
. : NA MRJD No.: See MRID table below DP Barcode: D425 I 80 R

egis trat i o n No.: 87895-1 Re g ul atory Act i o n: GDCI Revi ew Ca s e No.: 0140 CAS No.: 116-06-3 4 0 C FR : § 180 .269 FROM: William 

### H
. D o n ovan , Ph.D ., Che mi st Ri sk Assessme nt Branch V

# w.~/4.D~ H ea lth Effec t s Di v is io n ( 7 509 P ) THRO U GH: Danet1e Drew , Chem is ,

TO: Mi chae l Met z ger, Branc h' 

# f Ri s k Assess m e nt B ra nch 

### V /V II Health Effects Di v is io n (7509 P) Susan Bartow , Chem ic al Rev iew Manager Ri s k Manage m ent and Implementation Branch IV Pestic ide Re-evaluation Divis ion (7508 P) Office of Pe s ticid e Programs Tabl e A. MRID S umma ry T a bl e For A ldi c ar b. MRIO No. S tud y T y p e C omment s 4 815 6 901 860
. 1500 cotton field trial s 4815690 I .der.docx 48156902 860
. 1380 st o rage s tabili ty stud y 48156902
. der
. docx 48156903 860. 1340 ana lytica l methods 48 1 56903.der
. docx
In re s ponse to the aldicarb reregis tration data call-in of Jul y 2008 (G D C I- 09830 1- 27347) tha t r e q u ested cotto n and so rg h um field t ri a l stud ies a lon g with a supporting storage s tability study, Bayer Cro p Sc ie nce ( B CS) s ubmit te d the s tudie s li s t ed abo ve in Table A. PRO h as requested that H ED review th e studie s a nd determine i f th e s ubmi ss ion s adequate ly a ddr ess the relevant data gaps.
Page I of 9Aldicarb OCI Residue Chemistr y Review OP # 425 18 0
HED ha s prepare d Dat a Eva lu at io n Records (DERs) for the submitted studie s as li sted in Table A above. T hi s memo s umm arizes the regu latory implications resu ltin g fro m review of these studies. 

### Co nclu s i o n s H ED concludes that th e submi tt ed s tudi es are scie ntificall y re li ab le and adequate ly add res s the intended dat a gaps. As n o ted in th e aldicarb scopin g document ( 0 398520. C. Olinger 

### e t al., 5116 120 1 2) , BC S agreed to canc e l th e use on sorg hum , as annou n c e d in a Federa l R egister notice d ated O ctober 8 , 2008 (Volume 73 , N umb e r 196 , p p . 58958-58962). Therefore , the data o n sorghum are no longer requ i re d. The n e w cotto n field trial data sup p o rt the following update s to aldicarb tolerances in 40 C F R 

### § 180.269:

RAC C u rre n t R eco mm e n de d Com me n t To le r a n ce To lerance (ppm) (ppm) Co 11 0 11. 0. 10 0
. 20 In crease ba sed o n da ta in MRID 48156 90 1. und e linte d seed Co tt o n , g in 

## -- 0 .4 0 Value ba sed on data in MRID 4815690 I
. by product Co tt on. hulls 0 .3 0 R evo ke Co mm od it y cove red by th e raw agri c ultural co mmodit y to lerance ( 0266396
. C. Swartz
. 6 / 2/ 2000 ). The to lerance reco mm e ndati o n s in this m e m o are not expecte d to result i n significant c han ges to es tim ated di etary exposu res to aldicarb residues
. Although cotton raw agr icu ltural com m odi ti es (RACs) are li ves tock feedstuffs , re sidu e transfer to li vestock commodities is not expecte d ( i.e. , a 40 C FR 

### § l 80
. 6(a) ( 3) s i tuation applies). A hum an h ealth risk assessment is fo rthcomin g. 

### D e t a il ed Co n s id e r a ti o n s Analytical Methods (860.1340) 48 156903.der.docx Bayer CropScience s ubmitte d a hi gh performance liquid chromatography m e th od w ith tandem mass spectrome try detection (LC/MS/MS) , M ethod 00 8 51 , for the determination of residues o f aldicarb and it s m etabo lit es a ldi ca rb su l fo n e and ald icarb sulfoxide in potato e s and oran ge s . T he m e th o d was u se d fo r a nal ys i s of a ldicarb an d its metabolite s aldicarb s ulfone and aldicarb su l fox id e in the cotton m agnitude of the re s idue crop field trials and freezer sto rage s t ab ility stu di es. Briefly , samp le s we re extracted twic e with dichloromethane ( O CM):aceto n e (75:25 , v: v) and filtered. The extracts were combined and diluted with DCM/acetone. Ethy lene glyco l was added , a nd th e mixture was concentrat ed, recons tituted in acetonitril e an d diluted buffer (ammonium acetate a nd acetic ac id di l uted with water) , and filt ered. The filtrat e was diluted 10 time s using either the diluted buffer or the dilution mixture co ntainin g re serpi n e as inj ect ion standard fo r LC /MS / MS a n a l ys i s. The m e thod monitor s a s in gle io n tran s iti on fo r aldicarb (208 m/ z - 116 m/ z) , aldicarb sulfone (223 rn/z

- 76 rn/z), a ldi carb su lfo x id e (207 rn/z - I 32 m/z) , and r ese rpine (609.3 rn/z

- 195. l rn/z). The limit of quantitation (LOQ ; determined as the lowes t leve l of m ethod va l idation , LL MV) is 0.0 I ppm for e ac h anal y te. P age 2of9Aldicarb DCI Residue Chem istry Review DP# 425180

The method was adequate ly va lidate d using samples of potato, orange pulp , and ora n ge p ee l fortifi ed w ith eac h ana lyte at 0.01and0
. 10 ppm. Recove r ies were ge nerall y within the accep tabl e range of 70 -1 20% for all m atrices a nd analytes. 

### Conclusions H E D concludes that Method 00851 i s su it ab le for data collection purposes. The LC/MS/MS Method, 00851, was adequately va lid ated for determining re sidues of aldicarb and its metabo l ites a ldicarb s ulfoxide and a ld icarb s ul fo n e in potato, o ran ge peel , and orange pulp. The va lid ated 

### LOQ is 0.0 

### I ppm. The analytical procedure u se d in the storage stab ili ty and crop field trial stud ie s (M RID s 48156902 and 4815690 I , respecti ve ly ) h as been successfully va li dated for ald icarb in tenn s of s pecificity , linearity , precision , accuracy , and 

### LOQ. Storage Stability (860.1380) 48 I 56902.dcr.d o cx B aye r Cro pScience submitted a s torage stab ility st ud y w ith a ldi carb a nd it s metabolites a ldicarb su l foxide a nd a ld icarb sulfone in/on cotton und e linted seed and g in byproducts. Samp les of untreated com m odi ti es were fortified sepa rately wit h eac h analyte at 0
. 10 ppm , placed in frozen sto ra ge ( :S -20 ° C ) , and analyzed at sto rage inter vals of

- 0, 1 , 1.3 (see d only), 2, 4, and 5 month s (0, 27-28 , 38 (seed) , 55

- 56, 120- 1 2 1 , and 1 48-152 days). Be cau se decline was observed in/on co tton undelinted seed for res idu es of all three a n alytes fo ll ow in g I month of storage , add i tional samples of cotton undelinted seed we r e prepare d m idway through the stud y a nd w e re anal yzed at weekly s torage interv a l s of

- 0, I , 2, 3, 4, and 7 weeks ( 8 , 1 5, 22 , 28, and 47 days) to m ore accurately m o nitor loss o n s tora ge. 

### Conclusions The storage stability stud y with cotto n is considered scient i fically acceptab le. In th e 5- m onth st udy fo r cotton und e linte d seed, re s id ues of a ldicarb, aldicarb sulfox id e , and a ld ic arb s ulfone decli n ed fo ll ow in g I month of fr oze n sto rage, a nd ge n erally appeared to s tabili ze at s u bsequent storage intervals. In the 7

- week s tudy fo r und el inte d see d , lo ss on storage was o bs erved for residues of all three analytes at sto rage intervals > 1 5 days. When the r es ult s fo r both the 5- month and the 7-week studies are co mbin ed , the average recoveries for res id u es of a ld icarb, a ldicarb sulfoxide , and a ldicarb s ulf one in/o n cotto n undelinted seed at all storage interval s> 15 days we re 43-46% (ove rall ave rage rec overy for all three a nal ytes of

- 44%). The data for cotton g in byproducts indicate that residue s of a ldi carb were stab le during frozen s torage fo r up to 4 months but declined by the 5 -month storage interval (40% r ecove ry), w hil e residue s of a ldicarb su l foxide a nd ald icarb su l fone were s table for up to 5 month s. The subm itted storage stab ility data indicate that correction for loss on sto ra ge i s n ee d e d for resid u es of aldicarb, aldicarb s ul foxide , a nd aldicarb su lfon e in/on cotton undelinted seed s tore d frozen for > 1 5 days (44% recove ry] and for re s idu es of aldicarb in/on samp les of cotton g in byproducts sto red frozen for > 4 months [40% recovery].
Cotton Field Tr ial s (860. 150 0) 48156901.d e r.docx P age 3of9Aldicarb DC I Residue Chemistry R evie w DP ll 425 1 80



### Twelve fi e ld trials were conduc te d in the U nite d States durin g th e 2009 g rowin g seas on in th e North American Free Trade Agreement (NA FTA ) Growing Zones 2 (NC ; 1 tri a l) , 4 (AR, M O and MS ; 3 trials), 6 (TX; I trial), 8 ( OK and TX; 4 tri a ls), and l 0 (CA; 3 trials). At each trial loc a tion , th e treated pl ot rece ived two soil incorporated app li cat ions of a 15 % granul e (G R ) formulation of aldicarb (TEM IK l 5G). The first application was made at l . 2 - l .8 lb a i / A to bare so il at planting as a band ove r the open seed furrow th e n covered w ith soil, a nd the seco nd app lic a ti on was made between BBCH 52 (first floral buds v is ibl e) and BBCH 6 1 (begi nnin g of flowering ) at l .8-2.8 lb 

### ai lA as a s id e dr ess to a furrow to one s id e of th e plant row the n covered with soil. Th e tot a l seaso nal ap plic atio n rate was 3.0

- 4.5 l b a i / A. Ret re atmen t i ntervals ( R T i s) were 45

- 102 d ays. No adjuvants we r e u sed. Sa mpl es of seed cotton were h arv es ted at a targeted p reharvest interval ( PHI ) of 90 day s. Additional sample s we r e collected at th e O K trial at intervals preceding and following th e targe t 90-day PH I, at PH Is of 7 1 , 80 , 98, an d I 09 days , to inv es ti gate re s idu e d ecl in e . Fo r cotton g in byprod ucts , samp les at s i x trials were h arves ted using pi cker or s tripp e r eq uipm ent (3 tria ls each). Sampl es were a n alyze d for res idu es of a ldicarb , aldicarb sulfone, and aldicarb s ul fox id e u s in g hi gh performance liquid chromatography with tand e m m ass spec trom etry detection ( LC/ M S/MS), Baye r CropSc ience Method 0085 

### l. Residues of the m etabo lites were d ete rmin e d in parent equival e nts. Th e reported limit of qu antit ati on (L OQ ; determined as the lowest leve l o f method val id at io n , LLMV) was 0.0 I ppm for eac h ana lyte in cotton matrice s . R esu lts 

### Following two so il in co rp orated applic atio n s of the 1 5% G R formu la ti on m ade at total application rates of 3.0 -4. 6 l b ai / A , comb in e d residues of a ldi ca rb , a ldi carb s ulfone , and aldic a rb s ulfoxide we re <0.03- <0. 1 39 ppm in / on und e linted cotton s eed and < 0.03- < 0. 1 97 ppm inion gin byproducts. In the residue decline tri al , maximum combi ned residues of aldicarb , a ldi carb s ul fo ne, a nd aldicarb sulfoxi d e occu rred at the 80-day PHI in both und e linte d cotto n see d and g in b yprod uc t s, afte r w hi c h th ey decreased with in creasing PHI in g in byproducts. In seed, res i dues r ema in ed relatively s tabl e after the 9 0-day PHI. Sam pl es were stored frozen ( - -I O ° C) from h arvest to ex tracti o n for a nal ys i s of aldi c arb and it s metabolites aldicarb su lfone and a ldicarb s ulfoxid e fo r up to 1 33 days (4.4 months ) for unde lin ted cotton see d and I 3 6 day s ( 4 .5 m onths) fo r cotton g in byproducts. Samples were ana l yzed with in 2 day s of extraction. Acceptable storage stabili ty dat a ( 48156902.der) indicate that correction for loss on storage is needed for residues of aldicarb , a ldi carb s ulfo xide , and aldicarb sulfone i nion cotton undelinted seed s to r ed frozen for> 1 5 d ays (average recove ry of 44 % for eac h analyte fo r all s tor age inte rval s > 1 5 day s) and fo r res idue s of a ldi ca r b inio n sam pl es of cotton g in b yp roduct s sto r ed fro ze n for > 4 month s (40% recovery). Because residues of aldicarb were below th e LOQ inion a ll samp les of cotton undelinted seed and g in byproducts , the only corrections for l oss o n storage needed were for quantifiab l e res idu es of th e m e tab o lites i nion cotto n undelinted seed. Tabl e l s ummari ze d th e re s idue values from the co tto n tri a ls , co rr ecte d fo r sto r age l osses . Page 4 of9Aldicarb DCI Re s idue Chemistry Review DP# 425 180
Table 1. S u m mary of Res idues fro m Co tt o n F iel d T r i als w ith A ld icarb.

Crop Matrix Total Application PHI n ' Co mbined Re s idues 2 (ppm parent equivalents) Rate (days) Min. 3 Max
. 3 LAFT-' HAFT-' Median• Mean 4 

## so• ( lb ai /A) Co tt on 3
. 0 1-4
. 55 87 -11 7 12 <0
. 03 < 0. 19 9 <0
. 03 < 0.139 O.Q3 0.0453 0.032 1 undelinted seed Cotton 3
. 63-4.55 87 -11 7 6 <0.03 < 0.226 g in byproducts 1 n = number of field trials
. 2 C ombined r e s idue s of aldica rb , aldic arb s ulfone. and aldicarb su lfo xide
. 3 Valu es base d on t otal numb er of samp le s . <0.03 < 0
. 197 0 .05 02 0.0819 0
. 0677

4 Values based o n pe r-trial averages. LAFT = lowe st average field trial. HAFT = hi g hes t average field trial, SD= standard deviation
. For computation of the LAFT, I !AFT, median
. mean . and standard devi ation. values < LOQ arc ass umed lo be at th e LOQ (0.0 I ppm )
. 

### Conclusion s HED concludes that the sub mitted cotton s tudies adequately address the previously identified data gaps. Analysis of the results of the 12 new cotton trials (4815690 l.der) using the Organisation for Economic Co-operation and De ve lopment (OECO) tol erance calculation procedures re s ults in a s u ggested toleranc e of 0.2 and 0.4 ppm for cotton seed and g in byproducts , re spec tiv e ly (Appendix A and B ). Meat, Milk, Poultry. and Eggs (MMPE) (860.1480) The most recent evaluation of aldicarb residu es in MMPE commodities was provided in support of the Registration Eligibility Deci s ion 

### ( R E D) (D266396, C
. Swartz, 6/ 2/ 2000) , where HED concluded that re sidues in livestock commodities are classified under 40 CFR 

### § l80.6(a)(3) , 

### i. e., there is no reasonable expec tati on of finite residues. Becau se the submitted cotton field tr ial data s how detectable residues in cotton commodities , and these commodities may be fed to livestock , an update to th e previous determination regard in g livestock commodities is needed
. In a metabolism study (M RID No. 00159570) in which goats were dosed with 1 4 

### C-aldicarb for I 

### 0 days at 2.5 ppm , radi oactive residu es were as follows , with the residues of concern 

### (i.e. , carbamate metabolites) g iven in parentheses [aldicarb 

### p e r se was not detected in milk or tissues]: Milk (day I 

### 0): Live r: Kidney: Fat: Muscle: 0.12 ppm (0.0002 ppm ) 0 .5 2 ppm (0.00 

### I 4 ppm ) 0 .1 9 ppm (0.0006 ppm ) 0.02-0.03 ppm (not detected) 0.08 ppm (0.0002 ppm) In a poultry metaboli s m s tudy , hen s were dosed with non-radiolabeled aldicarb a nd aldicarb sulfone for 7 days , followed by 2 1 days of do s ing with radi o labe le d a ldicarb and aldicarb su lfo ne al 0
. 1 , I and 20 ppm in the diet. No res idues of concern were identifi e d in e i th er egg whites or yo lk s; following 20 ppm dosing , aldicarb su lfoxide was identified at 0.003 ppm in liver , and no other residues of concern were identified in li ver or o ther tissues. Table 2 summarizes th e tis s ueto-fe e d ratios determined from the goat and h en met a bolism studies.

Page 5of9Aldicarb DCI Re si due Chemistry Review DP# 425180
Table 2. S umm ary o f Coat and Hen Metaboli s m Studie s with A l di ca rb. Commodity Feeding Level, ppm Residue in Ti ss ue , ppm 1 Tissue-to-Feed Ratio Milk 2.5 0.0002 0
. 00008 Mu scle (ruminant) 2
. 5 0 .0 002 0
. 00008 Fat ( ruminant) 2
. 5 ND .. Liver (ruminant) 2
. 5 0 .00 14 0.00056 Kidne y ( rumin an t ) 2.5 0
. 0006 0 .00024 Eggs 20 ND 

### .. Mu scle ( poultry) 20 ND 

### .. Fat (po ultry ) 20 ND .. Liver (po ultry) 20 0.003 0 .000 15 Ski n/Fat (pou lt ry) 20 ND 

### .. 1 Maximum residue
. In addition to cotton , some rotationa l crop RAC s may be fed to li ves to ck. Previous review s of rotational crop s tudi es have concluded that detec table residue s may occur in rotational wheat and barley ( D200435 , 

### J. Garbus , 3 /20/ 1995) feed s tuffs. Spec ificall y , maximum residues of 0.88 and 0.60 ppm were found in rotational w he at forage and barle y forage , respectively. Although n o hay data we re provided , maximum residues may be estimated from the forage data by correcting for dry matter. Thu s, wh eat hay: 0.88 ppm 

## * (88/25) 

## = 3. l ppm and barley h ay: 0.60 ppm 

## * (88/ 30) 

## = 1.8 ppm. Using th ese values , livestock dietary burden s are estimated as shown in Table 

### 3. Table 3. A ldicarb Dietary B u rdens fo r Live s tock. More Balanced Di et (MBD) C r o p Co mm o dit y Type R esid u e % DM % Diet Di etary Co ntribution ppm 

## I input ppm

Beef Catt le Wheat 1 ll ay R 3. 1 HAFT 88 15 0. 53 Co tt on Meal PC 0.03 Median 89 5 0 .002 U

ntreat ed feed NA NA NA NA NA 80 0

T otal NA NA NA NA N A 100 0.53 D

airy Cattle Whcat 1 llay R 3.1 H AFT 88 20 0
. 70 Wh cat 1 Forage R 0. 88 HAFT 25 20 0.70 Barl ey 1 ll ay R 1.8 HAFT 88 5 0
. 10 Co tt on Unde linted seed PC 0.03 Me d ian 88 10 0
. 003 U

ntreat ed feed NA NA NA NA NA 45 0 Total NA NA NA NA NA 100 1. 5 1 Poultr y Cotton Meal P C 0.03 Median 89 20 0 .0 06 U

ntreated feed NA NA NA NA NA 80 0

Tota l NA NA NA NA NA 100 0.006 Swine Co tt o n Mea l PC O.Q3 Median 8 9 15 0.005 Un treat ed feed NA NA NA NA NA 85 0 Total NA N A NA NA NA 100 0
. 005 R

o tati o nal c r op.
Page 6of9A l d i ca r b OC I R es i due C h em i s t ry R ev i e w DP# 4 25 18 0 

### T he max imum res idu e lev el s e xpe cted in li ve s tock c o mmoditie s are es tima t ed a s a prod uc t of the a

pprop riate ti ss u e- to-f ee d rati os a nd d ietary burde ns as s hown in Tab le 4
. T ab le 4 . E s t im a ti o n of S eco ndar y R es idu es fro m U se o f A ld ic arb
. Co mm o dit y T i ss ue - t o - Fee d R a ti o Di e tar y Burd e n ( oom ) Ex pect e d R es id u e ( ppm ) M ilk 0
. 0 0 008 1.5 0.000 12 Mu s cl e (cattle) 0
. 00008 1.5 0
. 000 1 2 Fa t ( c a tt l e) 

### -- 1.5 

### -- Live r (c att le) 0
. 000 5 6 1.5 0.0 0 08 4 K id ney (ca ul e) 0.000 24 1.5 0.00 0 36 E ggs 

## - - 0
. 00 6 

### -- M u s cl e (oouh rv ) 

## -- 0
. 006 

### -- f at (po ult ry) 

## -- 0
. 006 

## -- Live r (po ult ry ) 0
. 000 15 0.0 0 6 0.0000009 Ski n/fa t ( o o uhry) 

### -- 0.006 

## -- Con clu s ions 

### HE D co nc lud es that 40 C FR § l 80 .6( a)(3) s till appli es to a ll M MP E co mm od iti e s s ince th e max imu m e xp ected res idue s are < 0
. 00 

### I ppm 

### [LOQ/ 1 

### O].

Att ac hm e nt s 48 1 56 901.de r .do cx [c otto n field tri a l s] 4 8 1 56 9 02
. der.docx [ c otto n s tora ge s tabili ty] 4 81 569 0 3 .der.docx [ an a l yt ic al meth o d]

Page 7 o f9Aldicarb OC I Residue Chemistry Review


### A pp e ndi x 

### A. OEC D Tol eranc e C al c ul ati o n s fo r A ldicarb/ Cotton Seed. Aldicarb Cotton Seed USA 3.5 lb ai / A, 90-day PHI Total nwnber o f data ( n ) Percentage of censored data Nwnber of non - censored data Lowest residue Highe s t residue Median res i du e Me a n St an d a rd devi a tion (SD) Co r re c tion factor for censoring (CF) Propo s ed MRL estimate

- Highest r esidue

- Mean + 4 SD

- CF x 3 Mean Unrounded MRL Ro un ded MR L

High uncertainty of MRL estimate
. [High level of censoring]
Re s idue s ( mg/kg) n < 0
. 03 8 0.0422 1 0.0538 1 0.0678 1 0
. 139 1



### Page 8of9 12 67%

4 0
. 030 0 .139 0
. 030 0.045 0
. 032 0
. 556

0
. 139 0
. 173 0
. 075 0 .1 73

0
. 2 O P# 425 18 0Aldicarb DC I Residue Chemistry Review
A pp e ndi x B . 

### OECD T olerance Ca lculations for A ldi carb/ Co tt o n Gi n Byp roducts
. Aldicarb Cotton Gin Bypd USA 3.5 lb ai / A, 90-day PHI Total nwnber of data (n) Percentage of censored data Nwnber of non-cen so red data Lowest residue Highest residue Median residue Mean Standard deviation (SD) Correction factor for censoring (CF) Proposed MRL estimate

- Highest residue

- Mean + 4 SD

- CF x 3 Mean Unrounded MRL Rounded MRL

High uncertainty o f MR L e s tim a te . (Small d a ta s et)
Residue s (mg / kg) n < 0.03 1 0.0334 1 0
. 0 413 1 0. 0 592 1

0
. 13 1 0. 1 97 1



### Page 9of9 6 17%"

5 0 .03 0 0.197 0.050 0 .082 0.06 7 0.889

0.197 0 .3 52 0.218 0.352

0 .4 DP# 425180Aldicarb [PC Code 09830 I]/Bayer CropS c ien ce 

### B
. 7.6 Res i d u es Res ul t in g fr o m S up erv ised T ri a l s (An n ex IIA 6
. 3; A nn ex IH A 8.3) 

### B .7.6. 1 Res idu es in Target C r o p s 

### B.7.6.1.1 Co tt o n D oc um e n t ID : MRID No. 4815690 I R epo r t : Gould, T. and Dall stream, K. (20 l 0) TEM IK l 5 G

- Magnitude of the Residue in/on Cottonseed and Cotto n Gin Trash. Report Numbers: RAA VX002 and M-385788-01-1. Unpub li shed study pre pared by Bayer CropSc i e nce . 312 p G ui de lin es: EPA OCSPP Harmo ni zed Test Guideline 860.1500 Crop Field Trials (Aug u s t 1996) PMRA R eg ulat o r y Directive OIR98-0 2

- Residue C hemistry Guidelines, Sec tion 9

- Crop Field Trials PMRA Regulatory Directive DIR2010-05

- Revisions to the Res idu e Chemistry Crop Field Trial Require ment s OECD Guideline 509 Cro p Field Trial (Se pte mber 2009) GLP Co mpli a n ce : No deviations from regulatory re quirements were reported which would have an impact on the validity of the study. Acce pt a bili ty: The study is considered scientifically acceptable. Th e acceptab ility of this st ud y fo r regulatory purposes is add r essed in the forthcoming U.S. EPA Res idue Che mi stry Summary D ocument , DP # 425180. Eva lu ato r: William H. Donovan , Ph.D. , Chemist , RABY No t e : Thi s Da ta E valuati o n R e co rd ( DE R

) was ori gi nall y prepared under contract by Vers ar. Inc
. (6850 Vcrsar Center. S prin g fi e ld. VA 22 151: s ubmitted 3/13 / 15 )
. The D ER h as been r ev ie wed by H E

D a nd re vi sed to reflec t c urrent Office of Pes ti c i de Prog ram s (O PP ) poli c ie s . 

### EXECUT I VE SUMMARY In response to th e Residue C hemi stry Chapter of the Aldicarb RED (DP# 266396, 6/ 2/ 00 , C. Swa rt z) , Baye r CropScience ha s sub m itted field tri a l data for aldi c arb on cot ton. Twelve field trials were conducted in the United States during the 2009 growing season in the North American Free Trade Agree ment (NA FTA) Grow in g Zones 2 (NC ; 1 trial), 4 (A R , MO and MS ; 3 trials), 6 (TX; 1 trial), 8 ( OK and TX; 4 trials) , and I 0 (CA; 3 trials). Each trial consisted of one untreated plot and one treated control plot. At each trial location , the treated plot received two soil incorporated applications of a 15 % granule (G R) formulation of ald icarb (TEM IK 15G). The first application was made at 1. 26- 1
. 79 lb ai / A ( 1.41- 2.0 I kg ai / h a) to bare soil at planting as a band over the open seed furrow then covered with soil, a nd the s econd application was made between BBCH 52 (first floral buds visib le) and BBCH 6 1 (beginning of flowering) at 1.7 5-2.76 lb ai / A (I .97-3.09 kg ai/ha) as a side dress to a furrow to one s id e of th e plant row then covered with so il. The total seasonal application rate was 3.0 1- 4.55 lb ai / A (3.38 -5.10 kg ai / ha ). Retreatment intervals ( RTi s) were 45-102 days. No adjuvants
EPA MRID # : 4815690 1 PMRA # : NA Pa g e I of 11Aldicarb [PC Code 09830 I ]!Bayer CropScience


### were used. Samples of seed cotton were harvested at preharves t intervals (PH Is) of 87-117 days. Additional samples were collected at the OK trial at intervals preceding and following the target 90-day PH I , at PHJ s of 71 , 80, 98, and 109 days , to in vestigate res i due decline. To produce the required samples of cotton gin byproducts , samples at six trials were harvested using picker or stripper equipment (3 tria ls each); samples from the remaini ng trial s were harvested by hand. All samp les were transported from the field sites to GLP Technologies (Navasota , TX) for generat ion of unde l inted cotton seed (all trials) and gin byproducts (s ix trials). Cotton was ginned with i n 36

- 92 days of harvest. Samples were either shipped under ambie n t cond itions within 1 day of harvest to the ginning faci l ity , where they were placed in frozen storage , or were maintained frozen at the testi ng facility and shipped frozen to the ginning faci li ty. All samples were shipped frozen to the analytical laboratory , where they were stored frozen until analysis. The storage intervals for samples between harvest and extraction we re 67-133 days (2.2

- 4.4 months) for undelinted cotton seed and 69- 1 36 days (2.3-4.5 months) for cotton gin byproducts. Samples were analyzed within 2 days of extract io n . Accep table storage stability data have been submitted (refe r to MRlD 48156902 ; B.7.6.2) in vestigating the stability of residues of aldicarb, aldicarb sulfone , and aldicarb su l foxide in/on cotton undelinted seed and gin byproducts during frozen storage for up 5 months. The data indicate that res idues of all three analytes were unstable inion cotton undelinted seed at storage intervals > 15 days. In cotton gin byproducts , res idues of ald ica rb were stable for up to 4 months but declined by the 5-month storage in t erval, while residues of aldicarb sulfoxide and aldicarb sulfone were stab le for up to 5 months. The subm itted storage stability data indicate that correction for loss on storage is needed for residues of aldica rb , aldicarb sulfoxide, and al dicarb sulfone i nion cotton undelinted se ed stored frozen for > 15 da ys (average recovery of 44% for each analyte for all storage intervals > 15 days) and for res idue s of ald icarb i n/on samples of cotton gin byproducts sto red frozen for >4 months (40% recovery). We note that, because residues of aldicarb were below the LOQ in/on all san1ples of cotton unde l inted seed a nd gin byproducts in the current study, the only corrections for loss on sto rage needed were for quantifiable residues of the metabo l ites in / on cotton un d elinted seed. Samples were analyzed for res idue s of a l dicarb , aldicarb sulfone , and a ld icarb sulfoxide using high performance liquid chromatography with tandem mass spectrometry detection (LC / MS/ MS) , Bayer CropScience Method 0085 1 with minor modificat ions . Residues of the metabolites were determined in pare nt equivalents by use of analytical standard solutions prepared in pare nt equi va l ents. Acceptable method val idation and concurrent recoveries were reported fo r samp les of cotton undelinted seed fortified with each analyte at 0.01-0. l 0 ppm and g in byproducts fortified with each analyte at 0.01-0.40 ppm, thu s validating the method. The reported limit of quantitation (LOQ ; determined as the lowest level of method val idation , LLMV) was 0.01 ppm for each analyte in cotton matrices
. The fort ification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels (within an order of magnitude for undelinted seed). Concurrent recoveries were corrected for apparent residues in controls if p r esent. Res idues in treated samples we re not corrected for residues in contro l s. Fo ll ow i ng two so il in co rporated applications of the 15 % GR formulation made at t o ta l app l icati on ra t es of 3
. 01

- 4.55 lb ai / A (3.38-5. l 0 kg ai/ ha) , combined residues of aldicarb , EPA MRID # : 48156901 PMRA II : NA Pa ge 2 of 11Aldic arb [PC C od e 09830 I ]/Baye r CropScience aldicarb sulfone, and aldicarb su lfoxid e (and per-trial ave ra ges) were < 0.03- < 0.199 (<0.03

- < 0 .1 39) ppm in/on undelinted cotton seed and <0.03- <0.226 ( < 0.03- < 0.197) ppm in/on gin byproducts. In the re s idue decline trial , maximum combined residues of a ldic a rb , ald icarb s ulfone , and aldicarb sulfoxide occurred at the 80-day PHI in bo th undelinted cotton seed and gin byproducts , after wh ich they decreased with increasin g PHI in gin byproducts. In seed , residues remained relatively stab le after the 90-day PH I. I. 

### MATERIALS AND METHODS A. MATERIALS

Table B.7.6.1.1-1. No m e n c l at ure fo r Aldicarb and its Metab o lit es o f In te r est. Co mm o n name Identity CAS n o. Co mpa n y experim e n ta l name Other synony m s (if ap pli cab le)

M e tabolite Ident ity CAS no. Co mpan y experime n tal nam e Oth e r sy no n y m s (if a p p li cab le)

Metabolite Id entity CAS no. Co mpan y experi men ta l n a me Other synonyms (if applicab le)

E

PA MRID # : 48156901 PMRA #: NA /\ l dicarb 2-M c th y l-2

- (meth y lthio)propionaldchydc 0- ( meth y l carbamoy l ) o x ime 11 6- 06 - 3 N

A NA CH 3 0 I 11 /H CHrS · C - CH = N - 0 -C - N I ' CH3 CH3 /\ldi carb s ul fo x id e 2-Mcth y l-2-(meth y lsulfin y l)propion a ldch y de 0

- ( m e th y l carb amoy l) oxim e 1 6 46 -87- 3 NA NA 0 CH 3 0 II 

## I II CH3S-C-C H =N- OCNHCH3 

## I C H 3 Aldi carb sulfone 2-Mcth y l-2- ( rn cth y ls ulfon yl) pro pion nld e hyde 0- (mcth y l carbamo y l) oxirne 1 64 6 -88-4 NA NA H3 C\ #0 C H 3 N - C 

## I I \ H 0-N = CH-C-CH:i 

## I O=S = O 

## I CH 3

Pa g e 3 of 11Aldicarb [PC Code 09830 I] ! Baye r CropScicncc 

### B. 

### S tud y D es i g n 1. 

### Test P roced ure Twelve residue trials on cotton we re conducted with a 15 % GR formulat ion of aldicarb (TE MIK I SG) during the 2009 grow in g season. Fie ld trial locations 

### by NAFTA growi n g zo ne are summari zed in Table 8.7.6.1.1-2. The trial s separated by <2 0 miles have been assessed for independence as detailed in the table below. 

### HED has determined that there are sufficient differences between the trials that they may be considered separate.

Independent Trial Determination 1 Trial Nos. Differenci.:s Deci s ion J\YO I0-09 11 A and Loca t ion: Sanger, CA vs. r=resno. CA Independent AVOl l-09HA Variety : PHY 725 RF (J\CALA) is a**Genuity ~**  Roundup Read)!® Flex convers ion of PHY 72 vs. Pl IY 755 WRF (ACALA) is a WidcStrike® I nsect Protection and Genuit -Y® Roundup Read yi> Flex conversion of PHY 72. Both have semi

- s mooth leaf type. medium t all plant height, very good se eding vigor. and high yield potential with adaptation across San Joaquin Valley
. Timing: 20

- day offset in planting/first soil application and 7 -d ay off set in harvest Soil type: Sandy loam vs. loam y sand (Note: Use pattern i s two soil app li ca1ions. lirst application made to bare soi l at planting and the seco nd is made as a side dres s to the furrow to one side of the plant row.) •No other dilTerenccs found in criteria. but note that PFI and testing faci lity are different for each trial: Car l E. Joplin of Sy n Tech Research In c. for AYO I 0-09HA and Brian D
. Lange of Euro!i ns Agroscience Services for AYO I 1-09HA 1 All assessments arc based on the replicate trial guidance prese nted in drafi memo 568_ Cri tcria for Independ e nce ofTrials 04 / 23/ 2013 (E PA and PMRA ). A separa te tank mix was used for all applications. Tab l e B.7
. 6. l.l -2. T ri al Numbers an d Geogra p h ical Locatio n s . Crop No. NJ\FT A Growing Zone T otal Trial s I 2 3 4 5 6 7 8 9 10 11 12 Cotton Sub
. I 3 I 4 3 12 Req
. 1 Ill 3/ 2 I /I 4/ 3 3 / 2 12 / 9 1 As per Table 5 of 860.1500 for cotton. TI1c seco nd number rcOects a 25% reduction 111 the number of trial s allowed for th e crop as a repre se ntative commodity in s upport of a crop g roup/ s ub g roup toleran ce or when application re su lts in no quantifiable re sid ue s. Per OCSPP 860
. 1 000 Supp l e ment (6/ 30 /08), cotton mu st be harvested by commercial equipment 10 provide an adequate representation of plant re s idue for the ginning proce ss. Three field trials for harvesting of s tripper collon are needed. No data arc needed fo r picker collon. Locations and detailed u se patterns for the trials are provided in T able B. 7.6. l.1-3.

Tabl e B. 7.6. 1.1-3. Study Use Pattern. Location: City, End -u se Sta te : Year Product 1 (Trial ID) Su nbury. NC; 15 %G R 2009 (A YOO l- 09HA)

EPA MR1D #: 48156901 PMRA # : NA M e thod of Application: Timing of J\pplication
I
. Soi l incorporated, banded to seed furrow: at planting, 13BCI I 0 2. Soil incorporated, side dre ss: B13CH 55 Yo lum e 2 Rate per (gal/ A) Application [Uha) { lb ai/A) [kg ai /ha] N IA 1 .794 12 .009 ] NIA 2.757 [3
. 088] Rctreatmcnt Total Surfactant/ Har vest Interval Rate Adjuvant Procedures (days) (lb ai /A) (kg ai/ ha]



### -- 4
. 551 None Picker [5
. 097( 59

Pag e 4 of 11Aldicarb [PC Code 09830 I )/ Bayer CropScience Tab le B.7.6.1.1 -3. S tud y Use Pattern. Location: City. End-use State: Y ear Product 1 (Trial 10 ) Pro ctor . A R : 15 % GR 2009 ( A V002

- 09 H A)

Fisk. MO: 20 09 15 %G R (AV 00 3-09HA)

G re envi ll e. MS: 15 % GR 2009 (AV004

- 09 1I A)

Eas t Bernard. 15 % GR TX: 2009 (A V 00 5-09HA )

Uva ld e. T X: 15 %G R 2009 (A V006

- 09 H A)

I l inton. OK; 15 %G R 2009 (A V007

- 09 DA)

Levelland. TX : 15 % GR 2009 (A V008-09HA)
Wolfforth, TX ; 15 %G R 2009 (A V009-09HA)

Sa nger. C A; 15 %G R 2009 (A VO I 0-09HA)

Fresno
. CA: 15 %G R 2009 (AV0 11- 09 H A)

E PA MRID #: 48156901 PMRA #: NA Me th od of Application: Ti min g of Application
1. Soil incorporated. banded to s eed furrow ; at planting , 13B C H 0 2
. So il incorpora ted , s ide dre ss: BBCH 5 9 I
. S oil incorporated. banded to seed furrow; at p lanting. Bl3 C H 0 2
. So il incorporated. side dres s ; OBCH 55 I
. Soil incorporated , banded to s ced furrow: at planting. BB C H 0 2
. Soil incorporated. side dre ss: BBC I I 59 I
. S oil incorporated. banded to seed fu rrow ; at planting. BB C H 0 2
. So il incorporated. side dress ; Bl3C H 60 I
. Soi l incorporated , banded t o seed furrow ; at planting , BBC H 0 2
. Soi l incorporated. s ide dre ss; OBC I I 52 I
. So il incorporated
. banded to seed furrow; at planting
. BB C H 0 2
. So il inco rporated. side dress ; BBCI I 60 I
. So il inc orpo ra ted. banded to see d furrow ; at planting, BBCH 0 2
. Soi l incorporated. s ide dre ss; BB C ! I 60 I
. So il inc o rporated , b anded to seed furrow; at planting , BB C H 0 2. So il incorporated , side dress ; OBCH 60 I
. So il incorporated. b anded to se ed f urro w: at planting. BBC H 0 2
. So il inc orpora ted. side dre ss; BBC I I 60 I
. Soil incorporated. banded to seed furrow: at planting , BB C H 0 2. Soil incorporated, side dre ss: OBC I I 61 Volum e 2 (gal/ A) [Uha] N

I A N

I A N

I A N

I A N

I A N

I A N

I A N

I A N

I A N

I A NIA N

I A N

I A
I A N

I A N

I A N

I A N

I A N

I A N

I A R ate per Retreatm e nt Total Surfactant/ H arvest Application Interval R ate Adjuvant Procedures

( lb ai/ A) (days) (l b ai l A) [kg ai/ha j [k g ai/ha]

1 .520 

## -- 3.680 None Picker [I. 70 41 [4.125] 2
. 16 0 45 [2.421] 1.551 

## -- 3.665 No ne Picker [I. 739] 14
. 10 8] 2
. 114 68 [2 .37 0] 1.530 

## -- 3.620 None Hand [1. 7 15] [4 .058 ] picked 2.090 46 [2 .343 ] 1 .570 

## -- 3.630 None Stripper 

### r 1. 160 1 [4. 069] 2 .060 5 1 [2 .309] 1.591 

## -- 3.691 None Stripper (1.784] [4
. 1 3 8] 2
. 100 60 [2 .3 54] 1
. 762 

## -- 4
. 1 50 None Stripper I 1 .97 5] [4.652] 2.388 69 [2.677] 1 .505 

## -- 3.604 None I l and [ 1. 687] [4 .040] picked 2 .099 61 [2 .353 ] 1.4 73 

## -- 3.572 None H and [1. 65 1] 1 4.005] picked 2
. 099 56 [2 .353 ] 1.4 29 

## -- 3. 5 79 None H and [ 1 .602] [4
. 012] picked 2
. 1 50 70 [2
. 411] 1 .504 

### -- 3.600 None H a nd [ 1. 686 ) [4 .036] pi c ked 2 .096 55 [2 .350 ]

Pa ge 5 of I IAldicarb [PC Code 09830 I ]/Bayer CropSc ic nce Table 8. 7.6. 1.1 -3. S tud y Use Pattern. Location : City, End

-u se Method of Application ; Volume 2 R at

e per Retreatment Total Surfactant/ Harves t State: Y ear Product ' Timing of Applica ti on (gal/A) Application Int erval Rate Adjuvant Pro cedures (Tri al 10) [L/ha] (lb ai/ A) (days) ( l b ail/\) [kg ai lh a ] [k g ai/ha ] Blythe, CA: 15%GR I
. Soil incorp orated , N IA 1 .260 

## -- 3.013 No ne Hand 2009 banded lo seed furrow; (1.41 2 ] [3
. 378] picked (A VO l 2

- 09HA) at planting. BBCH 0 2. Soi l incorporated. N I A 1. 753 102 s ide dress; Bl3CI I 5 5 [1
. 965] 1 15 % granule (G R ) formulati o n (TEMIK I 5G)
. 2 Sp ray vo lu me is not applicable (N/A) for g ranule ap plication
. Cotton was grow n a nd maint a ined according to typical agricultural prac ti ces . Irri gation was used to s upplement rainfall as needed. No unu s ual weathe r cond iti ons were rep o rt e d to have adverse l y affec te d crop production or yield during the s tud y. 

### Sa mpl e Hand lin g a nd Preparation Single control and duplicate treated samp l es of seed cotton were harvested at PHis of 87- 1 17 day s . A dditi ona l samples were co ll ecte d at the OK trial at intervals pre cedin g and following the tar get 90- d ay PHI , at PHi s of 71 , 80 , 98 , and 109 days , to investigate residue declin e . To produ ce the re quir ed sa mple s of co tton gin byproducts , samp les at s ix trial s were h arves ted using p icker o r stripp er equipment (3 trial s each) ; sample s fr o m the remainin g trials were har vested by hand. Sample sizes w e re**34** lb for stripper harvest ,**45** lb for picker harvest, an d**l** kg for manual collection. All sampl es o f seed cotton we re s hipp e d to OLP Technologi es (Navaso ta, TX ) for generation of cotton undelinted seed and gin byproducts. Sample s from Tri a l s A 

### YOO I and AV006 were sh ipp e d under a mbi e nt conditions with in 1 day of harvest by th e field cooperator or courier; sampl es from th e re m a inin g tri a ls we re pl aced in frozen s to rage at th e fi e ld s ites**within ~** 7 .5 h ou rs o f harvest and were s hipped via freeze r truck to OLP Te c hn o logies. A t OLP Tech nol og ies , sampl es were sto red froz e n (<

- 5 °C) prior to and following ge neration of cotto n undelinted seed and g in byproducts. San1p les of see d cotto n were cleaned with a s tick extractor to rem ove g in byproducts within 36-92 da ys of harv es t. Samples were s hipp e d frozen 4

- 27 d ays after g innin g to th e anal ytical laboratory , Pyxant Labs (Co lorad o Sp ring s, CO) for hom oge ni zation , extraction , and analysis , exce pt for samples from Trial A V005, which were s hipped fir s t to Bay e r Re searc h Park (BRP; Stillwell, KS ) and then sent to Pyxant L abs. At Pyx ant Labs , sampl es were maintain ed frozen (< -1 0 °C) prior to processing and ana lys is. In preparat ion for analysis, samp le s we re homogenized in the presence of dry ic e . 

### 2. Description o f A n a lytical P r oce dure s Sam pl es we re analyzed for residues of aldicarb , a ldi carb s ulfoxide , and aldi car b s ul fone u s in g LC/ MS /MS, Bayer CropScience M et ho d 0085 

### J with minor modification s . Modifications includ e d the following: minor procedural , material s, and instrument changes ; re m oval of reserpine as an internal standard ; optim iza tion of in s trum e nt parameter s a nd gradient; and monitorin g a di ffe re nt ion transition for quantitation of aldicarb su l fone to improve s ensitivity. A compl e te descript ion (including method valid a ti o n d ata) of this m ethod is provid e d in a se parate fil e (refe r to 48156903.der.docx). This m e th od was al so u sed for data co ll ec tion in the s torag e s tab ility st ud y (refer to 481 56902.der.docx). EP A MR1D # : 48156901 PMRA # : NA Pa ge 6of11Aldicarb [PC Code 098301 ]/ Bayer CropScicnce


### Briefly , samp l es were extracted twice with d ic hlo ro m et h ane (DCM):acetone (75:25, v:v) and filte r ed. The extrac t s we re co mbin e d a nd diluted with DCM / acetone. Et hy l e n e g l yco l was added , and the mixture was concentrated, reco n sti tute d in ace tonitril e, a nd diluted buffer (ammonium acetate and acet ic acid d il uted with water), and filtered. The filtrate was re-diluted w ith buffer for LC/MS / MS an a lys i s. R es idues of the m et abolites were determined in parent e quivalents by use of a n a l yt ica l s tandard so lution s prepared in parent eq ui va lents. The reported LOQ (determined as the LLMV) was 0
. 0 I ppm for each ana lyte in cotton m atrices. We note that the petitioner a lso presented calcu lated va lu es for the LOO ba sed on the recoveries obtained from samples Fort i fied wi th each anal yte at th e 0.0 I

- ppm fo rti fica ti on level. The LOD was ca lculated by multiplying the standard deviation of recovery measurements at th e LLMV by the one- tai led t-stat is tic at the 99% confidence l eve l for seven re pli cates and adding this to the average res idu e fo und in th e untreate d co ntro l. Th e calculated LODs fo r aldicarb , ald icarb su lfone , and aldicarb sulfoxide we re 0.0040 , 0.0054 , an d 0.0055 ppm , respec ti ve l y , in/on undeli n ted cotto n seed and 0.0034 , 0.0053 , and 0.0037 ppm , respectively, i nio n cotto n gi n byprod ucts. 

### II . RES UL TS AND DI SCUSS ION M ethod performanc e was eva luated during method val id at ion and by u se of concurre nt recovery s amples. For m ethod va lid ation , sampl es of und e linte d cotton seed and gin byproduct s w e re fortified w ith aldicarb, aldicarb s ulfon e, and aldicarb s ul foxi d e at 0.01 , 0. 10 (undelinted seed o nly ), and 0.40 ppm (g in byproducts only). For concurrent recovery , samples we re for tifi ed with a ldicarb , a ldi carb s ulfon e, an d a ldi carb s ulfoxid e at 0.0 1 ppm for undelinted cotton seed and at 0.0 I and 0.20 ppm for cotton g in byproduct s. Recoveries were ge n e ra ll y w ithin the acceptab l e range of 70-120 %; therefore , th e m e thod was considered valid for the analysis of a ldi car b , a ldi carb s ulfone , and al d i carb sulfoxide re si due s in cotto n matrices ( Table B.7.6.1.1-4 )
. The fortificat io n levels b racketed the m easure d residues (w ithin an ord e r of ma g nitude for undelinte d se ed )
. Co ncurrent recoveries were corrected for apparent res idu es in co ntr o l s if present. T he detector respon se was lin ear for aldi carb, aldi carb s ulfoxid e, and aldica rb s ulfone (coefficie nt of d e tennination , 

## r2 ::;: 0.9982) within th e range of 5-1000 n g/g. Representat ive chromatogram s of control samples , fortified samp les, and treated sa mpl es were provided. The co ntrol chromato grams ge n e ra ll y had n o pe aks of interest abov e the chromatograp hi c backg rou nd. The fortifi e d sam p le chromatograms contai ned only the anal yte of i n terest , and peaks were sy mmetrical a nd well d e fined
. A pp a r e nt res idu es in controls were below the LOQ (< 0.01 ppm ) for both m at rices. The rep orte d re s idu e va lu es were not corrected for apparent res idue s in controls. Re s idues of the metabolites were detenn i ned in parent equiva lents by use of analytical sta nd ard so luti o n s prepared in parent eq ui va le nt s.

E PA MRJD # : 4815690 1 PMRA # : NA Page 7of 11Aldicarb (PC Code 09830 I]/Bayer CropScie nce Tab l e B.7.6.1.1-4. Su mmar y of Method Validation a n d Procedural/Co n c u r r e n t R ecove r ies of Aldicarb , A l dicarb S ul fo n e, a n d A ld icarb S ulfoxide fr o m Co tt on Mat ric e s . Matri x Analyte Fonification Sample size Rccovcries 1 Mean ± S t d
. Dev . Level (ppm) ( n) (%) ( % ) Method vn lid ntion U

nde linted seed Aldicarb 0.0 I0

-0. 100 1 0 72- 106 9 1 ± 11 Aldicarb sulfone 0.010

-0
. 100 1 0 75 -1 06: 121 93 ± 14 Aldicarb sulfoxide 0
. 0 1 0

-0
. 1 00 1 0 56: 73 -104 83 ± 15 Gin by product s Ald i carb 0.0 I 0

-0
. 400 10 75-112 92 ± 13 Aldicarb s ulfon e 0.0 I 0

-0.400 1 0 72- 120 95 ± 12 Aldi carb sulfoxide 0.0 10

-0
. 400 10 66: 70 -1 00 83 ± 11 Conc urrent r ecoveries U

ndclintcd seed Aldicarb 0
. 010 18 79-98 92 ± 5.4 Aldicarb s ulfonc 0.0 10 18 75- 10 1 88 ± 7
. 8 Aldicarb s ul foxidc 0
. 0 10 18 70-93 80 ± 6
. 0 Gin byproducts Aldicarb 0.010

- 0
. 200 7 80-100 90 ± 8
. 9 Aldicarb sulfone 0.0 I0

- 0
. 200 7 74- 10 3 9 1 ± 11 Aldi car b su l fox id e 0.0 I0

-0.200 7 72 -1 00 87 ± 9
. 8 1 C o n c urre nt r ecoveries were co rrected for apparen t re s idues in co n trol s. Samples were s tore d froze n (

- -JO °C) from harve s t to extraction for analysis of aldicarb and it s m etabo lites aldicarb sulfone and a ldicarb su lfo xide for up to 133 days (4.4 months ) for undelinted cotton seed and 136 day s (4.5 months) fo r cotton gin b y products (Tab le 

### 8
.7 .6.1.1-5)
. Samples were analyzed within 2 days of extraction . A cceptabl e storage stability data h ave be e n submitted (refer to MRID 4815690 2) inve s tig at in g the stability of residu es of aldicarb , aldicarb sulfone, and aldicarb s ul fox id e i n/on cotton undelinted see d and gin byproducts during fro z en storage for up 5 m o nths. The data indicate that residues of all three analytes were unstabl e in/on cotton undelinte d se ed at s torage intervals > 1 5 days. In cotton gin byproducts , res idue s of aldicarb were stable for up to 4 months but declined by the 5-month storage inte r va l , w hil e re s idue s of a ldi carb sulfoxid e and aldicarb s ulfon e were s table fo r a t leas t 5 month s. The submitted storage s tability data indi cate th a t correction fo r loss o n s torage is ne e ded for re s idu e s o f aldicarb , aldicarb sulfoxide, and aldicarb sulfone in / on cotton undelinte d se ed stored frozen for> 15 days (ave rage reco ve ry of 44 % for each analyte for all s torage intervals > 15 days) and for res idue s o f aldicarb in/on sa mpl es of cotton gin byproducts stored fro ze n for > 4 month s (40% recove r y). We note that , becaus e residues of aldicarb were below the LOQ in/on all samples of cotto n undelinted seed and g in byproducts , th e only corrections for lo ss on s torage needed were for quantifiable residues of the metabolite s in/on co tt o n und e linted seed
.

Tab le B.7.6.1.1-5. S umm ary o f Storage Co n d i tio n s . Matrix Sto rag e Temperature Ac tu al Storage Int erval of Demonstrated S torage Stabilit y (o

C) Duration 1 Collo n, und elint ed <-5 at GLP 67-133 day s Re s idues ofaldicarb. aldicarb sulfox i de. and aldicarb seed Techno log ies (2
. 2-4
. 4 month s) s ulfon c were un s t ab le during frozen s tora ge in/on cotton <-I 0 at P yxa nt undelinted seed at s torag e int e rval s> 15 d ays. 2 Cotto n gi n 69- 1 36 days Re s idues o f aldicarb were stable durin g fro zen s t orage by

pro duct s (2
. 3-4
. 5 month s) for up t o 4 months but declined by the 5

-month s torage interval; r e s idue s of aldi carb sul fo xide and aldicarb s ulfon e were st able for up to 5 mo nth s. 2 1 Inter v al fro m harves t to extracti o n. Samples were ana l y zed w11hm 0-2 days of extracti o n . 2 Refer to 48 156 902.0E R; B
. 7.6.2
EPA MRID #: 48156901 PMRA # : NA Pa ge 8 o f1 IAldicarb [PC Co de 098 3 0 I ] / Bayer CropScience The res ults from the s ubmitte d field trials are presen ted in Tables B.7.6.1.1-6 and B. 7 .6. 1. 1-7. Fo ll owing two s oi l incorpo rated app li cation s of the 1 5 % G R formulation made at to ta l a pplication rate s of 3 .0 1 -4.55 l b ai / A (3.38

- 5. l 0 kg a i / h a) , comb in ed re s i dues of aldicarb , a ldicarb s ulfon e, and aldicarb su l foxide (and per- trial averages) were < 0.03- < 0. 1 99 ( <0. 03- < 0. 1 39) ppm in/o n und e l inte d cotton seed and <0.03

- <0 .22 6 (<0 .0 3

- <0. 197 ) ppm in/on gin byprod u cts . In th e res idu e d ecl ine tria l , maximum combined resi d ue s of a ld icarb, aldicarb sulfo ne , and aldica rb s u lfox ide occurred at the 80-day PH I in both undelinted cotton seed and gi n byproducts , afte r which they dec rease d w it h in c reasing PHI in gin byproducts. In seed , re s idu es remai ned r e lativ e ly s table after th e 90-day P H L
Tabl e B .7. 6
. 1.1

- 6. R es idu e D a t a fro m Cotto n Fi e ld Tri a l s with A l di carb. 1 Loca t ion: City, Zone Co 11on / State: Ye ar Variety (T rial ID) [ H a rves t Eq. ] Sunbury. NC: 2 DPL 445 BR 2009 [ Picker ] (A VOO 1- 09 1-lA )

Proctor, AR; 4 PHY375WRF 2009 [Picker] (A V002

- 09 H/\)

Fisk. MO : 2009 4 DP 1 64 B2RF (A V003

- 09 HA) [Picke r]

Greenvil le. M S: 4 DeltaPinc 2009 0935 BG ll /Rf (A V004

- 09 HA) E as t Bernard. 6 DP0924 B2F TX: 2009 [ S tripper ] (A V005

- 09 HA )

Uva ld e, TX: 8 DP 1 6 1 B2RF 2009 [ Stripper ) (A V006-091 I /\)

EPA MR ID # : 48156901 PMRA # : NA Matri x Rat e Pl-11 2 ( lb ai / A) (days) (kg ai/ha] Seed. 4
. 551 117 undelintcd [ 5.0971 G in byproducts Seed , 3.680 90 undelinted [4.125) Gi n byproducts Seed. 3.665 97 und c lintcd [4
. 108) G in byproducts Seed. 3.620 97 undclinted [4 .058 ]

Seed. 3.630 89 undelintcd [4 .069 1 Gin byproducts Seed. 3.69 1 87 und eli nt cd [4. 1 38 ] G in byproducts Re s idu es 3 (pp m parent equ iva l ents) [Average! Aldic a rb Aldicarb Aldi carb Co mbin e 5 Sulfone4 Sulfoxide4 D, N D, ND, <0.03, N D N D ND < 0.03 [<0.0 1] [ <O.O IJ [ <0.0 1] [ <0.03]

ND. ND. ND. <0.03, ND N D ND < 0.03 l < 0.0 1] [< 0.01] [ <O.O IJ [< 0.03]

ND. ND , ND , <0.03,

D ND ND <0.03 1<0.0 1] [< 0.0 1] [<0.0 1] [ < 0.03 1

ND, 0. 104. 0.0407. <0. 15 5. ND 0.0649 0.0305 < 0. 1 05 [ <0.0 1] [0 .0 8451 [0 .0356 ] [ <0. 1 30 ]

ND. N D , 0 .03 1 8 , < 0.05 1 8, ND ND 0.0639 <0.0839 1<0.0 11 [< 0.0 1) [0.0478] f<0. 0678)

ND. (0.006 84 ), 0.0408. <0.0608, ND (0.00802) 0.0376 <0.0576 [ <0.01) [ <0. 0 1] [0.0392] [<0.0592 )

ND , N D
. (0.00946). < 0.03, ND ND (0.00554) <0.03 [ <0.0 1] [ <0.0 I] [ <0.0 1) [ <0.03 ]

ND. ND. ND. < 0.03 ,

D N D ND <0.03 l <0.0 1] [ <0.0 1 1 [ <0
. 0 1 ] [ < O.OJJ

ND, (0.00656), 0.0 15 0, <0.0350, ND ND 0.0 11 7 <0.03 1 7 1<0.0 1] [ <0.0 1] [0.01 3 4] ( <0 .0334]

N D , ND, ND, <0.03, ND ND ND <0.03 [ <0.0 1] [ <0.0 IJ r<o.o n r<o.03 1

ND. (0.007 12), 0.0 1 82, <0.0382
. ND 0.0 12 0 0
. 0223 <0. 0443 [ <0.0 1 ) [<0.01 101 f0.0203) r< o.04 1 31

Page 9o f11Aldicarb [PC Code 09830 I ]/ B ayer CropScience Tab l e B.7.6 .1.1 -6
. Residue Data from Cotton Fie ld Tria ls w ith Ald icarb. 1 Location : City. Zone Cotton/ Matrix Rate PHl 2 State: Year Variety (lb ai / A) (days) (Tria l ID ) (1 larvest Eq
. I [kg ai/hal Hinton
. OK ; 8 FM 906382F Seed, 4.150 7 1 2009 [Stripper] undclinted 14.652) (A V007-09DA) 80
90
98
1 09
Gin 7 1 byproducts 80
90
98
109
Levelland. TX ; 8 fM9063 B2F Seed, 3.604 90 2009 undclintcd [4.040] (AY008-09HA) Wolfforth. TX; 8 327382RF Seed. 3.572 90 2009 undelinted [4.005] (A V009-09HA) Sanger, CA: 10 PHY 725 RF Seed , 3.579 88 2009 (ACALA) unde li ntcd [4 .0 12] (A VO 10-09!-IA} Fresno, CA; 10 PHY 755 Seed. 3.600 90 2009 WRF Acala undclintcd (4.036] (AYO 1 I -0911A) Bl ythe, CA ; 10 D&PL 164 Seed. 3
. 013 89 2009 B2RF undclinted (3.3 78 ) (AYO 1 2-09 1 I A) 1 A 15% granule (GR) formulation (T EMIK 15 0) of a l dicarb was used. 2 The target PHI i s ba lded for the decline trial. Residues' (ppm parent equivalents) !Avera ge ! Aldicarb Aldicarb Aldicarb Combine s Sulfonc4 Sulfoxide4 ND , ND. ND. <0
. 03. ND ND ND < 0.03 [<0.0 I] [ <0.0 1) [< 0.011 [< 0.031 0
. 0.0264, 0. 14 0, <0
. 176. ND 0.0266 0.1 55 < 0. 192 [ <0.0 1) 10.0265) [0
. 14 8] [ <0
. 184]

ND. ND. 0.0284 , < 0
. 0484. ND ND 0.039 1 <0.059 1 [ <0
.0ll [ <0
. 01) [0
. 0338) [ <0. 0538]

ND. ND. 0.0441 , <0
. 0641. ND NO 0.0357 < 0
. 0557 [< 0
. 011 [< 0
. 011 [0
. 0399) [ <0
. 0599)

ND. ND
. 0.0545, <0
. 0745. ND ND 0.0420 <0
. 0620 [ <0
. 0 11 [ <0
. 01] (0
. 0483] [ < 0
. 0683)

ND. 0.0388 , 0.120. < 0. 169. NO 0.0514 0
. 186 <0.247 [< 0
. 0 1] [0.0451] [0. 15 3 ] [ <0.208)

ND. 0.0592, 0.261. <0
. 330. ND 0.0758 0
. 306 < 0
. 392 [ <0
. 01] 1 0.0675) [0 .284] [ <0.3611 ND. 0.0247, 0. 1 34, < 0.169.

D 0
. 0352 0
. 181 <0
. 226 [ <0.011 [0 .0300 1 [0
. 157] [ < 0. 197]

ND, 0.0278, 0.148. <0. 186.

D 0
. 0283 0. 160 <0. 198 [ <0
. 01] 1 0.0280] [0.154] [ < 0
. 1921 ND, 0.0236 , 0.118. < 0
. 152. ND 0.0 195 0.1 1 2 < 0
. 142 [ <0.01] [0.0215) 1 0.115] 1 < 0
. 147] ND, ND. D. < 0
. 03. ND ND ND <0.03 [< 0.0 1] [< 0
. 011 [< 0
. 011 [< 0
. 031

ND. ND. ND. <0
. 03. ND ND ND < 0.03 [< 0
. 0 1 J f <0
. 01] [< 0
. 01] [ <0
. 03] ND. ND. (0
. 00683). <0.03. ND ND ND < 0
. 03 [ <0
. 01] [ <0
.01] [ <0
. 01) l <0
. 03]

ND, ND. 0.0595, <0.0795. ND 0.0520 0.137 < 0.199 [ <0
.01] 1 <0
. 03101 10
. 0983] [< 0
. 139] ND. ND. NO. <0.03, ND ND 0.0343 < 0
. 0543 [< 0
. 0 1] [< 0
. 0 1] [ <0
. 0222) [ <0.0422 ]

3 NO= Not detected (< LOO ). The LODs for aldicarb. aldicarb sulfone. and aldicarb sulfoxide, respectively, were 0.0040. 0.0054. and 0.0055 ppm for undelinted seed and 0.0034, 0.0053, 0.0037 ppm for gin byproducts. The LOQ wa s 0
. 0 I ppm for each analyte in both matrice s. Value s between the LOO and LOQ are reported in parenthesis. Combined residues and per tri a l averages were calculated by the s tudy reviewer using the LOQ for all residue s reported as < LOQ. Re s idu es of the metabolite s were determined in parent equivalen ts by u s e of analytical standard solutions prepared in parent equivalents
.
EPA MRID # : 48 1 5690 1 PMRA # :NA Page 10of11/\ldic arb [PC Co de 09830 I ]/Bayer CropScience •Quantifiable residues of aldicarb sulfone and aldicarb sulfoxide i n/o n cotton undelinted see d we re co rrected for lo ss on storage (calcu l a t ed as reported res idu t:/44% recov e ry) b y lhe s wdy reviewer and arc highlighted above
. 5 Combined residues of aldicarb
. a ld icarb su lfone. and aldicarb sulfoxide [which corresponds to th e residue defin iti o n for enforce ment purp oses !
.

Table B. 7 .6.1. 1 -7. Su mm ary of Re s id u es fr o m Cotton Fi e ld Trial s w ith A ldic a rb
.

Cro p M a lri x Total Applicalion P i ii nl Co mbined Rcs idu cs 2 (ppm parent equivalenls) Rate (days) Min
. 3 Max. 3 LAfT" H AFT4 Median 4 M ea n 4 ( lb ai/A) (kg ai/ha] Cotton 3.0 1 3-4
. 551 87-117 12 <0.03 <0. 1 99 <0.0 3 <0. 13 9 0.03 0.0 453 undelinted seed [3.378-5.0971 Cotton 3 .630-4.551 87-117 6 <0.03 < 0 .2 26 <0. 03 < 0.197 0.0502 0.08 19 gin by product s (4
. 069-5
. 097 1 1 n = number of fie ld trials. 2 Combined residue s of aldicarb. aldicarb su lfonc. and aldicarb s ulfoxide. 1 Values based on total number of sa mples. SD 4
0.0321 0.0677

• Value s based on per-trial averages. LAFT = l owest average field t rial, I ! AFT = hi g hest average field tri al, SD= s ta nd ard deviatio n . ro r compulation of th e LAFT , I !AFT
. median , mean . and s tandard deviation. va lu es< LOQ arc assumed to be at the LOQ (0
. 01 ppm)
. 

### III
. C ONCLU S IONS The cotton field trial s are conside red scientifically acceptable. Following two so il incorporated applicatio n s of the 15% GR formulation made at total application rates of 3.01-4.55 lb ai/A (3.38 -5.10 kg ai / ha) , comb in ed res idues of aldicarb , a ldicarb su l fone , and aldicarb su lfox id e (and per-trial averages) were <0.03

- <0
. 199 ( < 0.03- <0 .1 39) ppm i n/on undelinted cotton seed and < 0.03

- < 0.226 ( < 0.03- <0. 19 7) ppm in / o n gin byproduct s. Jn th e re s idu e declin e tria l , maximum combined residues of a ldicarb , aldicarb su lfone , a nd aldicarb s ulfoxide occurred at the 80-day PHI in both undelinted cotton seed and g in byproducts, after which the y decreased w ith increasing PH I in gin b yproducts. In see d , residue s remained relatively stab le afte r the 90-day PHI. An acceptab le method was used for residue quantitation , and adequate s torage stability data hav e been submitted to s upport sample s torage durations and conditio n s for a ll analytes. Ba se d on the result s of the storage s tability study , quantifiable re sidues of aldicarb s ulfo xide and a ldicarb s ulfone i n/o n cotton und e linted se ed were corrected for loss on storage (cal cu lated as r epo rt ed res idue/ 44 % rec ov ery)
. 

### R EFE R ENCES DP # 266396 , 

### 6 1 2 1 00 , C. Swartz ( Re s idue Ch e mistry Chapter of the Aldicarb RED).

EPA MRID #: 4815690 1 PMRA #: NA Page 11 of 11Aldicarb (PC Code 09830 l ]/Bayer CropScience 

### B.7. 6 R es idu es R es ultin g fr om S up erv ise d T ri a l s (A nn ex II A 6.3) B.7
. 6
. 2 S t a bili ty o f R es id u es Pri o r t o A nal ys is B.7.6.2. 1 Cotto n Doc um e nt ID: MRID No
. 48156902 

### Re p o rt : Seal , S. and Gould , T. (2010) Storage Stability of Aldicarb, Aldicarb Sulfoxide , and Aldicarb Sulfone on Cotto n seed an d Cotton Ginned B y Product s. Report Numbers: RAAVPOO 1 and M-385995-01-1. Unpublished study prepared by Baye r CropScience. 155 p. 

### G uid elin es : EPA OCSPP Harmonized Test Guid e line 860.1380 Storage Stability Data (August 1996) PMRA Regulatory Directive D IR98-02

- Residue Chemistry Guide l in es, Section 5

- Storage Stab ility D ata O EC D Guideline 506 Stability of Pe s ticide Residues in Stored Commodities (Octobe r 2007) 

### GLP Co mpli a n ce: No deviations from r eg ulatory requir emen t s were reported wh i ch would have an impact on the validity of the s tud y. 

### Acce pt ab ili ty: The study is considered scientifically acceptable. The acceptability of this study for regulatory purposes is address ed in the forthcoming U.S. EPA Re s idue C hemistry Summary Document , DP# 425 1 80. 

### Eva lu a t o r : William 

### H. D onovan , Ph.D ., Chemi s t , RABY Note: This Data Eva luati on R ecord ( D ER) was orig in all y prepared und er contract by Vcrsar. In c. (6850 Versar Center, Springfield. VA 2215 1 : sub mitted 3/13/15). The DER has been reviewed by HED and r ev ised to r e fl ec t current Oflice of P

es ticide Prog ram s (O PP ) policie s. 

### E X ECUT I VE SU M MA RY Bayer CropSc ience has submitted a s torag e stability study with aldicarb and its metabol i tes aldicarb s ulfoxide and aldicarb s ulfone on cotton undelinted seed and gin byproducts. Samples of untreated commodities were fortified separately with each ana lyte at 0.10 ppm , placed in fro ze n s torage (S

- 20 ° C) , and analyzed at s torage intervals of

- 0 , 1 , 1.3 (s eed only) , 2 , 4 , and 5 months ( 0 , 27-28, 38 (seed) , 55-56 , 120-121 , and 148-152 days). Because decline was observed i n/o n cotton undelinted see d for residues of all three analyte s following 1 month of storage, additional samples of cotton undelinted seed were prepa red midway through the stu dy a nd were analyzed at weekly s tora ge inte rvals of -0, 1, 2 , 3, 4 , and 7 week s (8 , 15 , 22 , 28, and 47 days) to more accurately monitor loss on s to rage. Samples were a naly zed for residues of aldicarb , aldicarb sulfoxid e, and aldicarb s ulfone using hi g h p erfo rmance liquid chromatography with tandem mas s spectrometry d etect ion (LC / MS / MS) , Bayer CropScience Method 0085 1 with minor modifications. Acceptabl e concurrent rec ove ri es were rep o rted for samp le s of cotton undelinted see d and gin byproduct s fortified w ith each a nalyte at 0
. 10 ppm , thu s va li dating the method. The reported limit of EPA MRID # : 48156902 PMRA #: NA Page 1 o f10Aldicarb [PC C ode 09830 I ] / Bayer CropScience 

### quantitation ( LOQ ; determined as the lowe st level of method validation, LLMV ) was 0.0 I ppm for eac h analyte i n co tt o n m atri ces. Co ncurre nt recoveries and recoveries in stored samples were corrected for apparent residues in controls. In the 5-month study for cotton undelinted see d , residues of aldicarb , a ldicarb s ulfoxide , and aldicarb sulfone declined fo ll owing I month of frozen storage ( r ecoveries of 31-33%) , and generally appeared to stab ili ze at subsequent storage intervals. In th e 7

- week study for undelinted seed, loss on storage was observed for residues of all three ana lytes at storage in t e rvals > 15 days
. When the results for both the 5

- month and the 7-week studies are combined, the average recov e r ies for r es idues of aldicarb , aldicarb sulfoxide , and aldicarb s ulfone in / on cotton unde lin ted seed a t a ll s to rage inte r va ls > 1 5 days were 43-46% (overall average recovery for all three analytes of

- 44 %)
. The data for cotto n gin b ypro ducts indicat e that residues of aldicarb were stab le during frozen storage for up to 4 mo nths bu t decli ned by t he 5-mo nth storage interval (40% recovery), while residues of aldicarb s ulfoxide and aldicarb sulfone were stable fo r up to 5 months. Th e submitted storage s tability data indicate that correction for loss on storage is ne e ded for re s idue s of a ld ica rb , a ldicarb su l fox ide , and aldicarb su l fone in/on cotton undelin ted s eed s tored frozen fo r > 1 5 da ys and for residues of aldicarb in/on s amples of cotton gin b y products stored frozen for > 4 months. 

### I. 

### MAT E RIAL S AND M ET HODS A
. MA TERIAL S 1. 

### Te s t M a t e ri a l Ta b le B .7.6. 2
. 1-1. Nom e n c l a tur e fo r A ldi ca rb a nd it s Me t a b o l it es of Int e r es t. Com mo n n a me I de nt ity CAS no. Co mp a n y ex p erim ental name O the r sy n o ny ms (if a 1 > pli ca bl e)

Metab o lit e Ide ntity CAS no. Co mpan y experim e nt al n a me Ot h er sy no n y m s ( i f ap p licab le)

EPA MRJD # : 48156902 PMRA #: NA Aldicarb 2-M eth y l-2- ( mcth yl thi o)p ropi onald chyd e 0- ( meth y l carba m oy l) ox im c 11 6-06 -3 NA NA C H3 0 I 11 /H CH r S · C

- C

H 

## = N -0- C - N I ' CH 3 CH 3
Aldicarb s ulfoxid c 2-M c thyl-2- (m e th y lsulfin y l)propiona l dehydc 0-(mcthyl carbamoy l ) oxime 164 6 -87- 3 NA NA

Page 2 of 10Aldicarb [PC Cod e 09830 l] fBayer CropScience Table B .7.6.2. 1

- l. No m e nclatur e for A ldic a rb and it s Met abo li tes of I nt e re s t. 0 CH 3 0 

### II 

## I II CH 3 S- C-CH = N- OCNHCH3 

## I CH 3 Met abo li te Aldicarb sulfone Id en tity 2-Mc1hyl-2

- (rnc1hylsulfonyl)propionaldchydc 0-(rncthyl carbarnoyl) oxirnc CAS n o. 1646-88-4 Com p any exper imental name NA Other syno nyms ( if app li cab le) NA H3 C 

### lo \ CH3



### N

-C I \ 

## I H 0-N=CH- C - C H:i 

## I O

=S = O 

## I CH 3 

### 2. Test Commodity Matri ces: Cotton undelinted seed and gin byproducts 

### B
. STUDY D ES I GN I. 

### Test Procedure Samples of untreated homogenized cotton und e linted seed and gin byproducts obtained from B ayer C ropSc ie nc e were separate l y fo rtifi ed wi th a ldi carb , ald icarb su lfoxide, and a ldicarb su l fone, each at 0.10 ppm, and placed in a freezer where they were stored at S

- 20 ° C from fortification until extraction and analysis. Day 0 sample sets i ncluded nine fortified samples (three replicates for each analyte), and two control samples. Analytical sets for each sto rage interval inclu ded two fresh fort ifi cation samp les, two s torage stab ility samp les for eac h anal yte, and two co ntrol samples. Samples of cotton und elin t e d seed and gin byproduc t s we re ana lyzed at storage i n tervals of

- 0, 1, 1. 3 (seed only) , 2, 4, and 5 months (0, 27-28, 38 (seed), 55-56, 120- 1 2 1 , and 148-152 days). Becau se dec li ne was obse rved in /o n cotto n und e linted seed fo r residues of all three analytes following 1 month of storage , additio n a l samples of cotton u ndeli nt ed seed were prepared midway through the study and were analyzed at week l y sto rage interval s of

- 0, I , 2, 3, 4 , a nd 7 weeks (8 , 15 , 22, 28, and 47 days) to more acc urately m on itor l oss on sto rage. The registrant noted that some of the stock so luti ons fo r the m etabolites were prepared in pa r ent equivalents and some were not. For th e cases i n whic h stock so lutions were not prepared in paren t equivalents, results were calculated in parent equivalents by the registrant using molecular we ight conversion factors
. The registrant reported recove r ed residues for th e metabolites both as unconverted val ues and conve rted to parent equ ivalents for all storage intervals. Because samp les were fortified separately with each analyte and because conversion to parent equ i valen t s EPA MR.ID #: 48156902 PMRA # : NA Pa ge 3of 1 0Aldicarb [PC Code 09830 !]/Bayer CropScience 

### ha s no impact on recovery va lu es, the recovered residu es for metabolites reported herein do not reflect conversion lo parent equivalents. 2 . De sc ription of A nal y tical Procedure s 

### Samples were analyzed for re sidues of a ldicarb , a ldic arb sulfoxide , and aldicarb sulfone using LC / MS/MS , Bayer CropScience Method 00851 with minor modifications. Modifications included the following: minor procedural , mate rials , and in s trument changes ; removal of reserpine as an internal standard; optimization of instrument parameters and gradi ent; and monitorin g a different ion transition for quantitation of aldicarb s ulfon e to improve se nsiti v ity. A complete descri ption (including meth od validation data) of this method is provided in a separate file (refe r to 48156903.der.docx). This method was also used for data collection in the cotton crop field trial study (refe r to 4815690 l .der. docx ). Bri efly, samples were extracted twice with dichloromethane (DCM):acetone (75:25, v :v ) and filtered. The extracts were combined and diluted with DCM/ acetone. Ethy lene glycol was added, and the mixture was concentrated , reconstituted in acetonitrile , and diluted buffer (ammo nium acetate and acetic acid dilut ed with water) , and fi ltered
. The filtrate was re -dil uted with buffer for LC / MS/ MS analysis. The reported LOQ (determined as the LLMV) was 0.01 ppm for each ana lyte in each matrix; th e limit of detection (LOD) was not reported. II. RESULTS AND DI SCUSS IO N 

### Method performance was eva lu ated by use of concurrent recovery samp les by fortifying untreated samp les of cotton undelinted seed and gin byproducts wi th each analyte at 0. 1 0 ppm. Rec ove ri es were within th e acceptab l e range of 70-120%; therefore, the method was considered va lid for the analysis of ald icarb , aldicarb sulfoxide , and aldicarb sulfone residues in cotton undelinted see d and gin byproducts. Refer to Table B. 7 .6.2.1-2a for the 5-month study and T able B.7.6.2.l-2b for the 7-week study. Concurrent recoveries were u sed to correct the recoveries in the stored samples. The detector response was linear for aldicarb , aldicarb sulfoxide, and a ldic arb sulfone (coeffic i ent of determination, 1 2**0.9908)** 

### within the range of 5

- 1000 ng/g. Representative chromatograms of control sampl es, fortified samples, and tre ated samples were provided
. The control chromatograms ge nerall y had no peaks of inte rest above the chromatographic background. The fortified sample chromatograms contained on ly th e analyte of interest, and peaks were symmetrical and well defined. Apparent residues in controls were <LOQ ( <0.01 ppm) inion both matrices. Concurrent recoveries and recoveries in stored samples were corrected for apparent res idues in contro ls if present. The registrant reported recovered re s idue s for the metabolites both as unconverted values and converted to parent equivalents for all storage intervals. Because sampl es were fortified separate ly with each analyte and because convers ion to parent equ ival ents ha s no impact on recovery va lu es , the recovered residues for metabolites rep orted herein do not reflect conversion to parent equivalents.

EPA MRJD # : 48156902 PMRA # :NA Pagc4ofl0Aldicarb [ PC Code 09830 I )/Bayer Cro pS cie nc e Tab le B.7.6.2.l-2a. Summary of P rocedural/Concurr ent Recoveri es of Aldicarb , Aldicarb Su lfox id e , a nd A ld icarb S ulfon e from Cotto n Matrices: 5-Mo nth Stu dy. Matrix A nalyte Fortifica tion S torage Int erva l , Level (ppm) ( Month s) Undelinted Aldicarb 0. 10 0 see d I 1.3 2 4 5 Aldicarb 0.10 0 s ulfoxidc I 1.3 2 4 5 Aldicarb 0.10 0 sulfonc I 1.3 2 4 5 G in A ldica rb 0.10 0 byproducts I 2 4 5 Aldicarb 0
. 10 0 sulfoxide I 2 4 5 /\ldicarb 0
. 10 0 s ulfone I 2 4 5 1 Concurrent recovenes were corrected for apparent residues in controls.**Standard** deviation is not applicable for sample sizes n < 3.

EPA MRID # : 48156902 PM RA #: NA Recoveries 1 (%) 12 0, 109. 107 98. 94 11 0. 11 4 87
. 90 74. 102 79.94 93, 8 1 , 81

84.87 8 6,96 85 , 75 90. 102 99.96 88 , 91. 85

94.88 89.82 70. 73 103, 102 96 ,93 120 , 116. 106

99, 114 97,93 102.92 98,90 96,99.95

87.83 80.80 79. 82 83 , 84 1 08, 101 , 106

92, 100 81. 73 96. 100 96.92 M ea n ± Std. Dc v. 2 (%) 112 ± 7.0 96 112 89 88 86 85 ± 6.9 86 9 1 80 96 97 88 ± 2.7

91 86 72 103 94 114 ± 7.2 106 95 97 94 97± 2. 1 85 80 80 83 105 ± 3.5 96 77 98 94

Page5ofl0Ald icarb [PC Code 09830 I ]/ Bayer CropScie nce T ab le B .7.6
. 2
. l

- 2b . S ummary o f Pr oce du r al/Conc u rr e nt R ecove ri es o f A ldi ca r b , Al d ica rb S u l fox i d e, an d A ld i ca rb S ul fo n e fr o m Co tt o n U n de li nt ed See d : 7 -W cek St u dy. Matrix Analyte Fortification Storage Interval Level (ppm) (W ee ks) Undclinted see d Aldicarb 0
. 10 0 I 2 3 4 7 Aldicarb 0. 1 0 0 s ulfoxide I 2 3 4 7 Aldicarb 0
. 10 0 su lfon e I 2 3 4 7 1 Concurrent recoverie s were corrected for apparen t residue s in controls. 2 Standard deviation is not app licable for samp l e s ize s n< 3
. Recoverie s 1 (%) 104. 107. 105 92,94 94.86 93.92 73, 108 108 , 1 09 I O

I , IOI, 11 3 104. 107 108. 106 95,90 77, 77 IOI , 99 97 , 102.99

104 , 11 0 106, 1 17 87. 94 1 04. 11 0 107. 112 Mean ± Std. Dev .2 (%) 105 ± 1.5 93 90 92 91 108 105± 7.1 106 107 92 77 100 99 ± 2.3 107 1 11 91 107 110



### The re s ults of the storage stability study a re presented in Tables B.7.6.2. l

- 3a (5-month study) and B.7.6.2. l

- 3b (7-week study). In the 5-month study for cotton undelinted seed , residues of a ldicarb , a ldicarb sulfoxide, and a ldicarb sulfo ne declined following I month of frozen storage ( r

ecoveries of 3 1 -33%), and generall y appeared to stabi l ize at s ubsequen t storage i nterval s. l n the 7-week study for undelinted seed, loss on storage was observed for residues of all three analytes at storage in tervals > 15 days
. When the result s for both the 5-month and the 7-week studies are combined , the average recove r ies for residues of ald icarb , aldicarb sul foxide, and a ld icarb sulfo ne in/o n co tto n u ndelin ted seed a t all storage intervals > 1 5 days we r e 43-46% (overall average recove r y for all three analytes of -44%). The data for cotton gin byproducts indicate that residues of a ldicarb were s table during fro ze n storage for up to 4 months but declined by the 5-month storage interval (40% recovery), while residues of aldicarb s ulfoxid e a nd a ldicarb su l fone were stable for at least 5 month s. The s ubm i tted storage stability data indicate that co1Tection for loss on storage is needed for re s idues of ald icarb, aldicarb su lfoxide, and aldicarb sulfone in/on cotto n undelinted seed stored frozen for> 15 day s and fo r residues of ald icarb in/on samples of cotton gin byproducts stored froze n fo r >4 month s .

EPA MRJD # : 48 156902 PMRA # :NA Pa ge 6of10Aldicarb [ PC Code 09 8 30 I)/ Bayer CropScie ncc Table B
. 7 .6.2. 1 -3a
. S t ab ili t y of A ld icarb , A ld icarb Su l fo xide , an d Aldicarb S ul fone Res idu e s in Cotto n Matrices Durin g Storage at
- 20 ° C for up to 5 month s . Commodity Analyte fortifica t ion Level (ppm) Undel intcd Aldicarb 0. 1 0 seed

Aldicarb 0.10 sulfoxide

Aldicarb 0.10 s ulfone

Gin Aldicarb 0.10 byproducts

Aldicarb 0.10 sulfox ide

Aldicarb 0. 1 0 su lfone



### . . 1 I

nte r val fro m fort tl1 cat1 o n to cx trac1 1 on .**~Co rrected**  for concurrent recovery .

EPAMR.ID#: 48 156902 PMR.A #: NA Storage l nterval 1 M o nth s (Days) 0 (0) I (27) 1 .3 (38) 2 (55) 4 (120) 5 ( 1 52)

0 (0) 1 (27) 1 .3 (3 8 ) 2 (SS) 4 ( 1 20) 5 ( 1S2) 0 (0) I (27) 1 .3 (38) 2 (55) 4 ( 1 20) 5 ( 1 52)

0 ( I ) I (28) 2 (56) 4 ( 1 2 1) 5 ( 1 4 8 ) 0 ( I ) I (28) 2 (56) 4 ( 121) 5 ( 1 4 8 ) 0 ( I ) I (28) 2 (56) 4 ( 1 2 1) 5 (148) Recovered R esidues Mea n (ppm) Recovery (%) 0. 1 20, 0. 1 09. 0. 1 07 11 2 0.0236, 0.0393 3 1 0.0299, O.oJ 16 3 1 0.0378, 0.0466 42 0.0697, 0.0559 63 0.03 8 3, 0.0368 38 0.0928
. 0.08 1 2
. 0.08 1 0 85 0.02 1 7, 0.0309 26 0.0273, 0.0300 29 0.0232. 0.0243 2 4 0.0469, 0
. 0346 4 1 0.0549 , 0.052S S4 0.0881, 0.0909, 0.08SS 88 0.027 1 , 0.0330 30 0 .0209, O.D25 I 23 0.0228, 0.0338 28 0.037 8 , 0.0640 5 1 0 .0 446. 0.0661 55 0.12 1 , 0. 11 6. 0. 106 11 4

0
. 09 1 2, 0
. 0943 93 0.0757, 0.078 1 77 0 .0 8 1 8, 0.0814 82 0.0353
. 0
. 0392 37 0.0955. 0.0993. 0.0947 97 0.0840, 0.0837 84 0.0736. 0.078 1 76 0.0913, 0.0791 85 0.0782, 0
. 07 4 7 76 0. 1 08, 0. 1 02, 0.106 105

0.0872, 0.0816 84 0.0750 , 0.0750 75 0. 1 02. 0.0905 96 0.0945, 0.0988 97 Concurren t Corrected Recovery Recovcry 2 (%) (%) 11 2 

## -- 96 33 11 2 27 89 47 88 71 86 4 4 85 

### -- 86 3 1 9 1 3 1 80 30 96 4 2 97 SS 88 

## - - 9 1 33 86 27 72 39 1 03 49 94 59 11 4 

## - - 106 88 95 8 1 97 84 94 40 97 

### -- 85 99 80 95 80 107 83 92 105 

### -- 96 88 77 97 98 98 94 103

P age 7of 10A ldi ca r b [P C Code 09 8 30 I]/ Baye r Cro pSc ie nce Table B .7.6.2. l -3b.S t ab ility of A ldi ca rb , A ld ic arb S ul foxide , an d Ald ica rb S ulfon e Re s idu es in Cotton Matri ce s Durin g Sto r a g e at
-20 ° C for u p to 7 weeks. Commodity A na lyte Fo rtifi cati o n Le ve l ( ppm ) Und e linted Aldi c arb 0
. 10 s eed

A ldi carb 0. 1 0 s ul fox ide

Aldicarb 0
. 10 s ulfone

1 I

nt erva l fr om fo rtifi ca ti o n to extrac ti o n . 2 Co rrec t ed for co ncurre nt recovery. S to rag e Int e rva l 1 R ecovered Re s id ues Wee ks ( D ays) ( ppm ) 0 ( 0) 0. 1 0 4
. 0
. 107 , 0
. 1 05 1 ( 8 ) 0
. 09 99. 0 .09 81 2 ( 15 ) 0
. 108 , 0
. 114 3 ( 2 2 ) 0. 049 7
. 0. 02 7 8 4 (2 8 ) 0
. 0400. 0.0334 7 (4 7) 0.0472. 0. 04 3 8 0 (0) 0. 10 1 , 0 .1 0 1 , 0
. 11 4 1 ( 8 ) 0. 1 01.0
. 10 1 2 ( 15 ) 0. 11 4
. 0. 1 20 3 ( 22 ) 0
. 053 7, 0
. 0489 4 ( 28 ) 0
. 0473. 0
. 0443 7 (47 ) 0.05 1 6 , 0
. 04 79 0 ( 0 ) 0.0 968 , 0
. 101. 0
. 0 989 I (8) 0
. 100 , 0. 109 2 ( 15 ) 0. 109, 0. 1 07 3 (22) 0.0 5 7 1 , 0.0606 4 ( 28 ) 0. 053 7. 0. 04 6 5 7 (47) 0.0 4 33 , 0.06 11 Mea n C o nc urren t Co rrected Reco v er

y Recover y Rccovery 2 (%) (%) (%) 105 105 

## -- 9 9 93 106 111 90 1 23 3 9 92 42 37 9 1 40 46 108 42 105 105 

## -- 10 1 1 06 95 11 7 107 10 9 5 1 92 56 46 77 59 50 100 50 99 99 

## -- 105 107 98 108 1 11 97 59 9 1 65 5 0 10 7 47 52 11 0 47 

### Graph s of the s to rag e s tability o f re sidu es o f aldi c arb , a ldic a rb s ul fox id e , and a ldi carb s ul fo ne duri ng froze n sto ra ge i nion co tto n und e linte d s e e d and g in b yp rodu c t s a re pre se nte d in Fi g ures B
. 7. 6
. 2 .1-l ( cotton und e linte d see d , 5-month s tud y), B
. 7 .6
. 2 .1-2 (cot ton und e linted see d , 7 -w ee k s tu dy), an d 8. 7.6
. 2. 1- 3 ( c o tt o n g in b ypro du c t s)
.

EP A MRJD # : 481 56 90 2 PMRA # : NA Pa ge 8of10A l d ica r b [P C Code 09830 I] / Baye r Cro pScie nc e Figure B.7.6.2 . 1-1 Graph of Aldicarb and Metabolite s in C otton Undelinted Seed S tored for up to S Month s

120 

# * 100 > Qj 80 > 0 u Cl) 60 0: -0 Cl) ..., u 40 Cl) '- 0 20 u 0 Storage Stabi lity of Aldicarb and Metabo l it es in Cotton Undelinted Seed

0 20 40 60 80 100 120 140 Storage Interval (Days)

_._.. Ald1carb - - Ald1carb sulfoxide _._.. Ald1ca r b Su lfone 160

Figure B.7.6. 2. 1-2 Graph of Aldicarb and Metabolites in C otton Undelinted Seed Stored for up to 7 Weeks

140 

# * 120 2:"' 100 Cl) > 0 80 u Cl) 0: -0 60 Cl) 

### u 40**~** 0 20 u 0 Storage Stability of A l dicarb and Me t abolites in Cotton Undelinted Se e d

0 10 20 30 40 Storage Int erval (Days) _._A ldi car b --<i Aldi carb sulfox1de -.- Aldicarb Sulfone

EPA MRID # : 48 156902 P MRA #: NA 50

Page 9of10Aldicarb [PC Code 09830 I ) / Baye r Crop Sc ic nce 

### Figure B.7.6.2.1-3 Graph of A l dicarb and Metabolites in Cotto n Gin Byproducts Store d for up to 5 Months

120 

### '*- > (jj > 80 0 u Q) 60 a:: "O**~** 40 u**~** .... 0 u 20 0 Stora g e Stability of Aldicarb and Metabolit es in Cotton Gin Byproduct s

0 20 40 60 80 100 120 140 Storage Interval (Days) -+-Ald i car b -+- Ald i car b sulfoxide ...,._ Al dicarb Sulfone 

### III . CONCLUS IO NS 160



### The storage stab ility study with cotto n is co n s idere d sc ientifically acceptable
. In th e 5-month s tu dy fo r cotton und e linte d see d , residues of a ldi carb, a ldi carb s ul fox id e, and aldicarb sulfone declined following l m o nth of frozen sto rage (recoverie s of 3 1- 33%), a nd ge n e ra ll y appeared to stab ili ze at s ub seque nt s tora ge interv a ls. In the 7-week study for undelinted seed, lo ss o n s t orage was ob se rv e d for res idu es of all thre e analytes at s tora ge interval s > 15 days. Whe n t he results for both the 5 -m o nth and the 7-week st udi es are co mbined , th e average rec over ies fo r residues of aldicarb , aldicarb s ulfoxide , and a ldi ca rb s ulfone in /o n cotton und e linte d seed at a ll s tora ge inte rva l s> 15 d ays were 43-46% (overall average recove ry for a ll thre e ana l ytes of

- 44%). The data for cotton gi n byproducts indic ate that residues of aldicarb we re s ta bl e during frozen s torage for up to 4 m onth s but declined by th e 5-mont h s tora ge inte rval (40% rec o ve ry ) , while residues of a ldi carb s ulfoxid e and aldicarb sulfone we re stable for at least 5 months. The subm itte d s torage s tability data indicate that correcti on for lo ss on stor age is n ee d ed for res idu es of ald icarb, aldicarb sulfoxide, a nd al di carb s ul fo ne i n/o n cotto n undelinted seed s to red frozen for > 15 days and for residues o f a ldic arb in/on san 1p les of cotto n g in byproducts s tored frozen fo r > 4 months. R EFE RENCES None
.

EPA MR1D # : 48156902 PMRA # : NA Page 10of10

# Volume 3 Annex B



# Aldicarb

B.5 METHODS OF ANALYSIS
B.5.2 ANALYTICAL M ETHODS FOR THE DETERMINATION OF RESIDUES (ALL COMPONENTS INCLUDED IN THE RESIDUE DEFINITION PROPOSED)Aldicarb [PC Code 09830 I) / B aye r CropS cience

Tabl e B
. 5.2- 1. Overview of t h e Ana l y tica l Method s for the D ete rmin a tion of A ldi carb Re s idue s. Dat a Matri x Analytes Method T ype Limit of R e f

e ren ce R

eq uirement Quantitation (ppm) Enforcement Not speci lied Total aldicarb GLC/FPD 0
. 0 1- 0
. 05 PAM Vol. II. Method s I Method s - Pl a nt re s idues detem1ined (Meth od 11) ( LOO) and II and Method s /I. Commodi ti e s as aldic arb s ul fo n e and B. Residue Cottonseed No t specified GL C

/ FPD 0 .02 Chemis tr y C hapt e r for (Method I s imilar to (LOO) Al d i

carb RED
. Method II ) DP#266396. C. Swartz. Co tton seed Not speci fied Co l orimetri c 0.03 6/2 / 00 (Method A) ( LOO) Oranges Not specified GC/F PD ot specified (Meth od B. si mil ar to Method II excep t no npolar GC column used) Data

- Gathe ring Potat o Aldicarb LC/MS/MS 0.01 S tu dy No
. MR-085/04 Method- Plant Orange pe el A ldicarb su l foxide MRID 48156903 Commoditie s Orange pulp Aldicarb sulfone P

o tato tub ers Aldicarb HPLC 0
. 02
. for each Re s idue Chemi stry Aldicarb s ulfo xid e (Me th od RPA C SOP a n alyte C h ap t er for Aldicarb Aldicarb sulfone 90015) (LOD = 0.0 I ppm ) R .EO, DP#266396. C. Swart z, 6 /2

/00 Enfo r ce m ent Milk No t spec ified GLC/ FPD 0.00 1 PAM Vol. II
. M e th od Method

- (Method Ill s imil ar to ( LOO) Ill , Re sidue Chem i s try Livestock Method II ) C hapter for Aldicarb Commoditie s RED. DP #266396. C. Swartz
. 6 /2

/00 Multiresid ue FDA -P esticide Re s idue C hemi s try Method Testin g Analytical Method s C hapt e r for Aldicarb Multi-Re s idue te stin g RED
. DP#266396. C
. program Swartz. 6 /2

/00 Table B .5.2-2. C h e mical S t ruc tur es o f A n a ly t es Ad dresse d b y Met h o d s for the An alys is of Ald ica rb
. Method ID Chemical Name 0085 1 Aldicarb

Aldicarb s ulfoxidc

EPA MRJD #: 48 1 56903 PMRA # : NA Ch em i ca l Structure C H 3 0 I 11 ,.H CHrS · C - CH = N- 0-C-N I ' CH 3 CH3

0 C H 3 0 II 

## I II CH 3 S-C-CH=N-OCNHCH;s 

## I C H 3

Pa ge2o f6Aldicarb [PC Co de 09830 I) / Baye r Cro p Sc ie nc e Table B.S.2-2. C hemical Structures of Ana lytes Addres se d by Methods for the Analy s i s of Aldicarb. Method ID C he mical Na me C hem ic a l Struct ure Aldicarb s ulfon e 

### H 3 

### C\ 

# /'° C H

3 N-C 

## I / \ H O - N=CH - C - CH 3 

## I O=S=O 

## I CH 3 No te : This Data Eva luation R ecord (DER) was originally pre pared und er contrac t by Versar, Inc
. (6850 V e rsar Ce nter , Sprin gfie ld. VA 22 1 5 1 ; subm itlcd 3/ 1 3/15). The D E R h as b ee n r eviewed by I IED and r ev ise d to re flect curren t Office of Pesticide Program s (O P P) p o li cies. 

### B.5.2.1 Analytica l Methods for Plant Matrices (Annex IIA 4
. 3 , Annex IIIA 5.3) B .5. 2.l .1 Post-Registration Method (Enforcement) Not Applicable 

### B.5.2.1.2 Pre-Registration Method (Data-Gathering) Document ID: MRID No. 48156903 

### Report: A nalytical M e thod 00851 for the Determination of Re s idu es of Ald i carb and It s Metabolites Aldicarb Sulfone and Aldicarb Su l foxide in Potatoes and Oran ges by LCMSMS. R e port Numbe r: MR -08 5/ 04. U npublished st

udy pre pared by Bayer CropScience. 57 p. 

### Guide lin es: EPA OCSPP Harmonized Test Guidelin e 860.1340 Residue Anal ytical Method (August 1996) PMRA Reg ulatory Dir ective DIR98-02

- Re s idu e Chemistry Guidelines, Sec tion 3

- Residu e Analyti cal Met hod EU SANCO 825 / 00/ re v . 7 ( 17/ 3/ 04) OECD Gu id ance Document on P est ic id e Re s idue Analytical Methods 

### GLP Compliance: No deviations from regu l atory requirement s were reported wh ich would have an impact on the validity of the study
. 

### Acceptabi li ty: The study is con s id ere d scientifically acceptab le . The acceptab ili ty of this s tud y for regulatory purposes is addressed in the forthcoming U.S. EPA Re s idue C hemi s try Summary Docume nt , DP# 425180. 

### Evaluator: William H. Donov an , Ph.D. , Chem ist, RABY 

### EXECUTIVE SUMMARY B aye r Cro pScience ha s s ubmitted a hi g h p e rfonnance liquid chromatograp h y method w i th tand e m ma ss s p ectrometry detecti o n ( LC/MS/MS) , Method 0085 1 , for the d e termination of res idu es of aldicarb and it s metabolites ald icarb su l fone and ald icarb s ulfoxid e in potatoes and oranges . The m e thod was used for analysis of aldicarb and it s metabolite s aldicarb s ulfone and a ldic arb su l fox id e in the cotton magnitud e of th e residue crop field trials and freezer s tora ge stab ility studi es . A complete method description and valid ation data were submitted
.
EP A MRID # : 48 156903 PMRA # :NA Page 3 of6Aldicarb [ PC Code 09830 I)/ Bayer CropSc i e nce B r iefly, s ampl es we re ex tra cte d t w ic e w ith di c hl o ro m eth ane ( D CM) : ace to n e (75 : 25, v : v) and fi lte re d . T he ex trac t s we re co mbin e d a nd dilut e d w ith D CM/ac e to n e. E th y le ne g ly c o l w a s a dd e d , and th e mixture was c onc e ntrate d , rec on s titu te d in a c e tonitril e a n d dilut e d bu ffe r (ammonium ac e ta te a nd ace tic acid diluted w ith wa t e r

), a nd filtered. Th e filtr a t e w a s dilut e d 1 0 tim es u s ing e ither th e d il ut e d buffer or th e dilution mi x tur e containin g rese rpin e a s inj e cti o n s ta nd ard fo r LC/ M S/MS a n a l ys i s. The m e th o d m o nit o rs a s in g l e ion tran s iti o n fo r aldicarb (2 0 8 

### mlz--+ 11 6 m /z), a ldi carb su l fo n e (223 m/z--+ 76 m/z), a ldi ca rb s ul fox id e (20 7 m /z --+ 1 32 m /z), a nd r ese rpin e (609.3 

### mlz--+ 1 95. l m/z ) [ interna l s tan dard ]. T he limit of qua ntit a ti o n (LOQ ; determ in e d as the lowes t leve l o f m e tho d va li da tion, LL M Y) i s 0.0 1 p p m fo r eac h anal yte. The m etho d was a d eq u a t ely va lid a t e d u s in g sam p les of po ta to, oran ge p ul p, a nd o range p ee l fo rti fie d w ith e a c h a n aly te at 0 .0 1 a nd 0 .1 0 ppm. Recove ri es we r e ge nera ll y w ith in th e acce ptab le ran ge of 70-1 2 0 % for all matric es and a n a ly te s. IL V data we re n o t s ubmi tte d to th e A ge nc y; howeve r , b eca u se I L V is no t ge ne ra ll y r e quire d fo r d a ta co ll e cti o n m e th ods, n o a d d iti o n a l in fo rm ati o n is re quire d.
l. 

### Principle of the Method: Method 00851 Tabl e B
. 5.2. 1.2-1. Summary Parameters for the Pre-Regi s tration Analytical Method U s e d for the Anal y si s of Aldicarb Re s idues in Potato , Orange Peel , and Orange Pulp. Me th od ID Analytc(s) Extraction solvent and technique
Clean-up strategics Instrument and Detector

Standardization method Stability of std solutions

Retention times

EPA MRID # : 4 8156 90 3 PM RA #: N A 0085 1 /\ l

dicarb. Ald i carb sulfoxide, and Aldicarb sulfonc Samples were extracted twice with dichloromethane (OCM):acetonc (75:25. v:v) and filtered. Tite extracts were combined and diluted with DCM/acetone. Ethylene glycol was added. and the mixture was concentrated, reconstituted in acetonitrile and diluted bufTcr (ammonium acetate and acetic acid diluted with water). and filtered. The filtrate was dilu t ed 10 times using either the diluted bufTer or the dilution mixture (diluted bufTer with I ug/L re serpine) for analysis. None I IPLC/ MS/MS using a Phenomcnex AQUA C 18 co l umn (and gradient mobi l e phase of water wit h 1. 5% acetic acid and ammo ni um acetate JO m M, and acctoni t ri l

c . MS/ MS de tec tion operated in pos iti ve io ni za tio n m ode under mu ltipl e re ac ti o n m on it o ri ng (MRM) con dit io ns. T he fo ll ow in g ion tra ns iti o ns arc m o nit ored: /\ldicarb: m l =208-+ 11 6 /\ldicarb sulfoxidc: 111 / ::: 207-+ 1 32 /\ldicarb sulfone: m l = 223-+76 Re serpine: 111 / : 609.3-- 1 95. I External standardization using a 6-point calibration curve to generate a s tandard curve through linear regression analysis. Standard stock solutions ( I000**~1g/ml).** fortification standards (I 0 and 1.0 μg/ ml )
. and calibration s olutions of aldicar b. in acetonitrile were reported to be stable for 2 months when stored at 5 ± 3 ° C. /\ldicarb sulfoxide and al clicarb sulfonc stock so lu ti ons were reported to be s table for 6 m

o nt hs when sto r ed at 5 ± 3 ° C. f-i nal extrac ts s tor ed at I0 ° C were fou nd to be s table for up to 7 days for potato. 3 days for orange pulp. and 4 days fo r orange peel. Al

dicarb

- 5.9 minutes Aldicarb sulfoxidc

- 2.8 minutes /\ldicarb sulfone -4.0 minutes R

e serpine -5.9 minute s

Page 4 of6A ldicarb [PC Code 09830 I) / Bayer CropSc ience 

### II. S p ec ificity The LC/MS/MS m ethod is hi g hl y selective for the quantitation of a ldi carb and its metabolites aldicarb su lfoxide and aldica rb su lfon e. Analysis of control samp les re s ulted in no signifi ca nt signa ls at the expected retention times of the analytes. The petitioner indicated that there was no interference wi th other substances observed at the ret ention time s of aldicarb and it s metabolites ald icarb su l foxide and a ldicarb su lfon e above 30% of the LOQ. The following ion transiti o n s are monitored: Aldicarb Alidcarb sulfoxide Aldicarb sulfone Re se rpine


### III. Linearity 

### nzlz 208-116 ( quantitation ) 

### m

lz 207-132 (quantitation) 

### m

lz 223-76 (quantitation ) 

### m

/

z 609.3-195. l (quant it ation) [internal s tandard]

For each analyte , the lin earity of detector response was evaluated using solvent s tandard solutions. Calibration c urve s we re calculated by linear r eg ression analysis with l / x weighting. For th e least- s quares eq uation , which descr ibes the detecto r resp o n se as a function of the standard conc e ntration , calibration curves resulting from the inj ec tion of a minimum of 6 standards over the concentration rang e of 0.04-5 

### μg/L demonstrated linearity with coefficients of determination 

### (r2) of at le ast 0.9990. 

### I V. Accu r acy (Recovery) and Precision (Repeatabil i ty) No radiovalidation dat a were included in the submiss ion. Analytical methods should be radi ova lidated to determine whether total toxic re s idue s (TTR) are extracted from weathered matrices. The method was adequately validated fo r the quantitation ion transition using samples of potato , orang e peel , and orange pulp fort ified w ith either a mi xed standard or each analyte separat ely at 0.0 I a nd 0.10 ppm. Recoverie s were generall y within the acceptable range of 70-120 %. The indi v idual recove ries were within the range of 67 -117 %. While there were two recoverie s from a total of I 08 m easureme nt s that were 67%, the mean recover ies were at least 70% w ith relative standard deviations S 20%. At the 0.01 ppm level ( LOQ ), the me an recoveries were within the ran ge of78 -1 00%, with relative standard deviations within the range of2.3

- l5%. At the 0.10 ppm level (1 Ox LOQ) , the mean recov eries were within the range of 83-102%, w ith relati ve standard devi ations within the range of 1.6-7 .5%. Repeatability data were gene r ated from at l east 18 samples fortified at the LOQ and at least 18 samp les fort i fied at I Ox LOQ fo r each matrix and analyte. The s tandard deviations ( RSD s) obtained for eac h fortification level were less than 20%. Recovery and re peatability data are presented in Table B.5.2.1
. 2-2 , below. Tab le B.5.2.1.2-2. Accurac y and Precis ion Data for Method 00851. Anal ytc Matri x Aldicarb P o tato EPA MRID # : 48156903 PMR A #: NA Fortification Leve l ( ppm ) 0.0 10 Co ncurrent Recovery( %) lndi v idual 1 Mean 67,88,83.86, 89,84 83 RS D Ran ge (%) 67 -89 9.8 Page 5 of6Aldicarb [PC Code 09830 I) / Bayer C r opScience T a bl e B.5.2. 1 .2-2. Accu r acy a nd Prec isio n D a ta for Method 0 085 1. Analyte Matrix Fortification Concurrent Recovery (%) RSD Level (ppm) Individu al' Mean Ran ge (%) 0.100 81. 84, 77 .82. 95, 80 83 77-95 7.5 Orange peel 0.0 10 89 , 99, 99, 1 03. 99. 98 98 89-103 4.8 0
. 100 92.94.90,89.93. 102 93 89-102 5.0 Orange pulp 0.0 10 91. 73. 83 , 9 1
. 83, 82 84 73-9 1 8.0 0.100 90, 91 , 91. 87, 92, 93 91 87-93 2.3 Aldicarb Potato 0.010 117. 83. 83 , 84, 86 , 90 91 83-117 14.6 su lfoxide 0.100 104, 102, 91, 97, 96, 85 96 85-104 7.3 Orange peel 0.0 10 88.83. 84.87.87 , 86 86 83-88 2
. 3 0. 1 00 102 , 102. 99, 100 , 104, 97 10 1 97-104 2.5 Orange pulp 0.0 10 89.67. 74 , 80. 78 .8 1 78 67-89 9
. 4 0. 100 84,84. 86,85, 90. 90 87 84-90 3.2 Aldicarb sulfone Potato 0.0 10 95.83,83.86, 80. 74 84 74-95 8
. 3 0
. 100 96 , 96. 98. 99 , 98, 100 98 96-100 1.6 Orange peel 0
. 010 95. 104. 100. 104. 98, 98 10 0 95-104 3.6 0
. 100 103. 1 06. 100 , 98. 102, 105 1 02 98-106 2
. 9 Orange pulp 0
. 010 92. 75. 95.94. 92. 93 90 75-95 8.3 0
. 1 00 94.99. 94,91 , 97,95 95 9 1-99 2.9

' The fir s t five rec ove ry re su lts were fortified with a mixed s tandard and the last result ( boldcd ) was fortified with each compound sepa ratel y. 

### V. Limit of Quantitation

Tab l e B .5 .2.1.2-3. S ummar y o f De t ectio n a nd Quant ita ti on Lim its for Meth o d 008 5 1. Analyte Matrix LOD (ppm)' LOQ (ppmf Aldicarb Potato Not rep orted 0 .0 1 Orange peel Orange pulp Aldiearb sulfoxide Potato Not reported 0.01 Orange peel Orange pulp /\ ldi carb su lfone Potato Not reported 0.0 1 Orange peel Orange pulp 1 LOO = limit of detection, no val ue reported. 2 LOO = limit of quantitation, determined as the lowest l eve l of method va li dation (LLMV). 

### VI. C onclu s i on s 

### T he LC/ MS / MS Method , 00851 , was adequately validated for determining residue s of ald icarb and its metabolites ald icarb sulfoxide and aldicarb sulfone in potato, orange peel , and orange pulp
. The validated LOQ i s 0.0 I ppm. The analytical procedure used in the s tora ge s tability and crop field trial studies (MRl Ds 48156902 and 48 1 56901 , respective ly) has been successfu ll y val idated for aldicarb in terms of specific ity , linearity, precision , accuracy, and LOQ.

E PA MRID # : 48156903 PMRA # :NA Page 6 of6