### UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460

OFFICE OF PREVENTION, PESTICIDESAND TOXIC SUBSTANCES 

### MEMORANDUM
DATE: June 17,2008
SUBJECT: 

### Drinking Water Degradates IdentificationMemorandum for Spirotetramat (PC Code 392201)@P353728)



### FROM: Jos6 Luis Melhdez, Chemist Environmental Risk Branch V 

### Environmental Fate and Effects Division (7507P)


### TO: George Kramer, Ph.D., Senior Chemist Registration Action Branch I Health Effects Division (7509P)
This memorandum identifiesthe environmental degradates of spirotetramatthat may be of exposureconcern for drinkingwater assessment. These data areprovided to help inform determinations of which environmental degradates are ofrisk concern for drinkingwater assessmentin support of human health risk assessment. If you have questions about this memorandum,please e:mail Jos6 Meldndez or contact at 787-977- 5856 or 787-799-3021. Spirotetramat (Table 1)is a new systemicbroad spectrum insecticide intended for the control of sucking pests. It belongs to the chemical class oftetramic acid derivates (ketoenoles). According to the label, it is active primarilyby ingestion against immature insect life stages and fertility of adult female insects maybe reduced. Spirotetramat moves "through phloem and xylem to all plant tissues includingnew shoot, leaf and leaf growth.. 

# ." This active ingredient is advised to be used as 

## "a preventative treatment or timed to coincide with early threshold level in developing populations." The products MOVENTOTM, 

### BY1 8330 150OD and ULTORTM are formulated as a suspension concentrate or 

### as 

## an oil dispersion containing 1.25lb a.i. per gallon or 2 lb a.i. per gallon, respectively. The maximum total application rate in a season is 0.4 lb a.i./A. The chemical may be applied by air, ground equipment or through chernigation.
Two stereo isomers of spirotetramat, cis- and trans-isomer, arepossible. The cis-isomer is the active substance.IWAC: cis-3-(2,5-dimethylpheny1)-8-methoxy-2- oxo-l-azaspiro[4.5]dec-3-en-4-y1 ethyl carbonate

8-methoxy-2- oxo-l-azaspiro[4.5]dec-3-en-4-yl



### All the following appear to be major routes of degradation1transformation for spirotetramat: hydrolysis in basic media, photolysis in natural water and biodegradation in aerobic and anaerobic environments (DT5O's range 4-23days). Hydrolysis in neutral and acidic environments and photolysis in sterile water (8.6-32.5 days) areroutes oftransformation of less importance. Spirotetramat degrades to spirotetramat-en01 (product of cleavage ofthe ester link), which also degrades moderately rapidly in aerobic environments and under photolytic conditions, and subsequently forms numerous degradates most of which have thebasic backbone structure of spirotetrarnat (themost important are spirotetramat-ketohydroxyand spirotetramat-MA-amidein soils). It appears that spirotetramat's residues may be of higher concern than 

### the parent due to spirotetramat's lability. Spirotetramat's residues have a potential to contaminate surface waters for a period of weeks to months posttreatment, and a relatively low potential to move subsurface and contaminategroundwaters. Spirotetramat has a moderate solubilityin distilledwater (33.4 mg/L) and a high solubility in various common organic solvents. Spirotetramathas a low vaporpressure and Henry's Law constant (4.2~10-l1 mm Hg at 20°C and 6.90 atm-rn3/mol at 20°C and pH 7, respectively). It is not likely to volatilize substantially. Spirotetramat's 1- 

### octanoVwaterpartition coefficientis 324, indicating a low tendencyto bioaccumulate.
The hydrolysis behaviour of spirotetramatis stronglypH and temperaturedependent. The rate ofreaction increased with increasingpH. At 25"C, the experimental half-lives for the chemical were 32.5, 8.6 and 0.32 days at pH's of4,7 and 9, respectively. In addition, hydrolysis rates increased with increasingtemperature. The major hydrolysate is spirotetramat-enol,which appeared to be stableto hydrolysis in this and in a separate study conducted on the metabolite at pH's 4,7 and 9 and 25°C. Spirotetramat photolyzes relatively rapidly. Spirotetramatphotolyzes with hydrolysiscorrected half-lives (DT5O's) of 3.0 and 0.22 days, in sterile buffer (pH 5) solution and natural water (pH 7.9), respectively. These half-lives (DT5O's) correspond to 9.3 and

### 0.50 days, respectively, under environmental conditions (summerlight in Phoenix, 

### AZ). In sterilized natural water the major products observed were 

### spirotetramat-enol(81.9% at 1 day), methoxycyclohexanone(17.5% at 8 days) and methoxy-cyclohexylamino carboxylic acid (1 1.3 % 

### at 10days). 

### In sterile buffer solution 

### (pH 5), the major transformation products were spirotetramat-photo-cyclopentyl(maximum 42.9% at 7 days), spirotetramat-photo-methyl(maximum22.9% at 6 days), spirotetramat photoformyl (maximum 11.5%at 3 days) and spirotetramat-photo-methyl(maximum 19.3%at 

### 6 days). All these metabolites are the result of rearrangement ofthe parent. The soil photodegradation study availableon spirotetramatwas found to have certain deficiencies. Definite conclusionson the rate of photodegradation could not be derived fiom it. However, useful informationon the identity of the degradates in the study may be obtained fiom the study. The following degradateswere identified: spirotetramat-en01 (maximum 10.1% at 1 day), spirotetramat-ketohydroxy

### (maximum 20.9% at 2 days), methoxycyclohexanone (maximum 10.0% at 2 days) and dimethylbenzoicacid (maximum 4.8% at studytermination, 7 days). Methoxycyclohexanone and dimethylbenzoic acid were observed only in the irradiated samples.
The major degradation pathway for spirotetramatunder aerobic soil condition is hydrolytic cleavage ofthe esterbond, yielding spirotetramat-en01(theoretically quantitatively). The latter is oxidized at the benzylic carbon to spirotetramatketohydroxy (maximum24.0% at 1 day), which is hydrolyticallyopened to spirotetramat-MA-amide(maximum 5.2% at 1 day, one sample). In anotherpossible pathway, demethylation of spirotetramat-en01 occurs to yield spirotetramat-desmethylen01 and subsequently spirotetramat-0x0-enol. Furthermore, oxidative spirotetramat-en01 dimerization may occur to yield spirotetramat-en01 dimer 1 and spirotetramat-en01dimer 2. Spirotetramat degraded under aerobic conditions very quickly, with half-lives (DT5O's) of <l day in four soils. Furthermore, spirotetramat-en01also degraded very quickly, with calculated half-lives DT5O's) of <l day in a separate study, in 

### four soils. The half-lives DT5O's) for spirotetramat-ketohydroxy(range 1 -5-1 6.7 days) and spirotetramat-amide (range 0.03-5.4 days) were calculated fiom the results obtained in the study conducted on spirotetramat-enol. Carbon dioxide formation was 9.7-19.4% by 50 days in the study conducted with spirotetramatand 10.9-34.9by 60 days in the studyconducted with spirotetramat-enol. Volatiles were insignificant while non-extractableresidues were important (both cases). In an outdoor metabolism study spirotetramatdegraded with calculated half-lives (DT5O's) of 1.2 and 2.9 days. Spirotetramat-en01 was a maximum of 7.8%. The degradates spirotetramat-glyoxylic amide and dimethyl-benzoic acid were observed besides the aerobic soil metabolites. The lattertwo compounds were also observed in the soil photodegradation studies.
In 

### aquatic environment, under aerobic aquatic conditions, spirotetramat degraded with calculated half-lives (DT5O's) of 0.7 and 0.9 days in 

### the total system. Spirotetramatwas initially mostly associated with the aqueous phase. The metabolite spirotetramat-en01 reached a maximum at 14days at 99.0%, and decreased to 

### <LOQ to 21.O% at 120days.

### The degradate 

### spirotetramat-ketohydroxy was a maximum of 50.8% at study termination. It appeared to be relatively stable in the aerobic aquatic system. Minor transformation products included spirotetramat-MA-amide, spirotetramat-0x0-en01 and spirotetrarnatdihydroxy 

### (58.7%in total system). Non-extractable residues increased throughoutthe studyto a maximum of 33.9% at 120days. Mineralization was a maximum of 13.5- 24.0% at 120days.
In the anaerobic soil metabolism study, the metabolites observed were also generally consistent with the ones for the aerobic soil metabolism studies for spirotetramatand spirotetramat-enol,

### with respect to the metabolites observed. Under these conditions, spirotetramat dissipated quickly with a calculated half-life of <<I day. The major degradates were spirotetramat-enol, which increased throughout the study (maximum 54.6% at 180days) and spirotetramat-ketohydroxy(maximum 19.3% at 1 day). Mineralization was very low. Non-extractable residues were a maximum of 1 7.5% at 0.6 days. In contrast, in an anaerobic aquatic metabolism system, spirotetramat completely degraded to spirotetramat-enol, which was found to be stablethereafter. The half-life for (DT50) the transformationof spirotetramatwas calculated to be 2.8 days in the total anaerobic system. Spirotetramat is moderately mobile in five sterilized soils, with 

## &values ranging from 3.58-5.52 mLlg, 

## Gc values between 184-437mL/goc (mean 289 mLlgoc), KFvalues ranging from 3.70-4.79 (pglgoc)l(pglm~)lln, KFoC values ranging fi-om 1 59-43 5 (pglgoc)/(pglm~)'" [mean 28 1 (pglgoc)/(pglm~)l"], ranging from 0.823 to 1.042 [(mean 0.941 (pglgoc)/(pg/m~) lIn)l. Spirotetramat-enol, 

### spirotetramat-ketohydroxyand spirotetramat-MA-amidewere found to be more mobile than the parent, spirotetramat. The mobility of spirotetramat-en01was assessed using a soil column leaching study. The chemical was found mostly in the 0-6 cm soil depth (9.6-16.5%) and at low levels in the 6-12 

### ern soil depth (0.1-1.4%). 

### In the leachate fractions, spirotetramat-en01 was a total of 0.1-2.8%. The estimated 

## bc values for spirotetramat-en01were between 27-99 mL/goc (mean 55 mL/goc) over four soil types (mobile). No definitive batch equilibrium test couldbe conducted on spirotetramaten01because the chemicalwas labile during the adsorption phase. The degradate 

### spirotetramat-ketohydroxyis mobile in five sterilized soils, with 

## &values ranging fi-om 0.529-2.28 mLIg, Koc values ranging fi-om 43.1-99.7 mL/goc (mean 65.3 mL/goc), KF values ranging fi-om0.516-2.21 (pglg)/(pg/m~)ll~ KFoC values between 41.O-99.1 (pglgOc)l(pglm~)l"[mean 63.7 (pg/goc)l(pglm~)l/n] and l/n values close to unity (range 0.915-0.929, mean 0.922). The 

## Gc values were similar to the Freundlich adsorption constants KFOC. The degradate spirotetramat-MA-amideis highly mobile in five viable soils, with 

## &values ranging fkom 0.064-0.179 rnLIg, results ranging fi-om4.2-25.6 mL/goc (mean 9.6 mLlgoc), 

## &values ranging fi-om 0.075-0.179 (pglg)l(pglm~)lln, KFoc values 4.4-25.5 (pglgoc)/(pglm~)lln [mean 9.3 (pglgoc)l(pglm~)l~n] and llnresults from 0.80- 1.07 (mean 0.95, for four of the five soils the range 0.93- 1.07). The Koc 

### results for the degradates spirotetrarnat-en01 dimer 1 and spirotetramat-en01 dimer 2 were estimated using HPLC methods in supplemental studies. The respectivemean values were 1624mllgoc and 3208 ml/goc (both are slightlymobile).

### Spirotetramat, at approximately0.39 lb a.i./A, formulated as an oil dispersion, was applied once to four plots (most of which included bareground and planted, total of 7 trials), located in the USA (FL, CA, NY and WA), dissipated rapidly with calculated half-lives of 0.3-1.0 days. These half-lives are consistent with the ones observed in laboratory trials. No carryoverfrom year to year is expected for spirotetramat. Due to the low storage stability of spirotetramat-enol, which degraded to spirotetramatketohydroxy during storage, individual quantification ofthese metabolites is not possible. Instead, the combined residues of spirotetramat-en01 and spirotetramat-ketohydroxy 

### were calculated. Those residues presented calculated half-lives (DTSO,s) of

### 4.6-3 1.6 days. 

### In addition, the combined residues of spirotetramat, spirotetramat-en01and spirotetramatketohydroxy were found to degrade at moderate rates with half-lives @T50,~) ranging from 5.0-23.4 days. Spirotetramatand its residues remained in the top 0-15 cm soil layer, except for detections in the 15-30 cm soil layer at the Florida site; the chemicals observed above the LOQ 

### in 15-30 cm soil layer were spirotetramat-en01 and spirotetramatketohydroxy at days 1 and 7. The residues went below the LOD and the LOQ by the next test interval.
Since this is a new chemical, there are no monitoring data available. The effects ofwater treatment on the pesticide and degradates is uncertain. Spirotetrarnat and its major metabolites, spirotetramat-enol,

### spirotetramat-ketohydroxyand spirotetramat-MA-amide, were highly mobile to moderatelymobile, and low levels ofbinding are expected. It appears that spirotetramat metabolites spirotetramat-ketohydroxy 

### and spirotetramat-MAamide are ofhigher concern because the parent and spirotetramat-en01degrade relatively fast in most environments (particularly in aerobicmedia). Spirotetramatis not readily biodegradable.
The followingtablespresent physico-chemical and fate data ofinterest to the Health Effects Division (HED).

Anaerobic soil:

Hydrolysis (pH 7): 91.8 Photolysiswater: 81.9 Aerobic waterlsed.: 79.7 / 41.2Spirotetramatketohydroxy

Spirotetramatdi-hydroxy

Spirotetramatdesmethyl-enol

Spirotetramat0x0-en01 CAS: cis-3-(23- Dimethylpheny1)-3- hydroxy-8-methoxy-lazaspiro[4.5]decan2,4-dione

IUPAC: 2 cis-1 

## - [[(2,5- Dimethylpheny1)hydr oxyacetyl]amino]-4-methoxycyclohexanecarboxylic acid

IUPAC: (5s,8~)-3- (23- dimethylpheny1)-3,4- dihydroxy-8-methoxy-lazaspiro[4.5]decan2-one

IUPAC: (5s,8~)-3-

dihydroxy-lazaspiro[4.5]dec-3- en-Bone

IUPAC: 3-(2,5- dimethylpheny1)-4-hydroxy-lazaspiro[4.5]dec-3- ene-2,8-dione ierobic soil: 24.0 Aerobic outdoor: 25.3 Anaerobic soil: 19.3 =ieldsoil: naa Soil photolysis: 20.9 iydrolysis: Jhotolysiswater: 4erobic waterlsed.: 17.4 1 42.8

4erobic soil: 5.2 4erobic outdoor: 6.2 4naerobic soil: 7.2 Field soil: 4.5 Soil photolysis: Hydrolysis: Photolysiswater: Aerobic waterlsed.: 7.8 12.1

Aerobic soil: 

## . Aerobic outdoor: Anaerobic soil: 3.2 Fieldsoil: Soil photolysis: Hydrolysis: Photolysiswater: Aerobic waterlsed.: 4.3 15.5

Aerobic soil: 2.0 Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysis water: Aerobic waterlsed.: 

### -

Aerobic soil: Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysis water: Aerobic waterlsed.:

## -. - 

## . 

# . . - 

## . - IUPAC: 2.5- Dlmernyl-DenzO'c Dimethyl-benzoic u 150.18 acid acid CH,

Spirotetramatglyoxylic amide

Methoxycyclohexanone

Methoxycyclohexylaminoc

arboxylic acid

Spirotetramat0x0-ketohydroxy IUPAC: (ls,&)-1- w5- dimethylphenyl) (oxo)acetyl]amino~ 4-methoxycyclohexanecarboxylic acid Aerobic outdoor: 3.3 Anaerobic soil: Fieldsoil: Soil photolysis: 21.8b Hydrolysis: Photolysis water: Aerobic waterlsed.: 

### -

Aerobic soil: Aerobic outdoor: 2.3 Anaerobic soil: Field soil: Soil photolysis: 4.1 Hydrolysis: Photolysiswater: Aerobic waterlsed.: 

### -

IUPAC: 3-(2,5- dimethylphenyl)9-hydroxy-lazaspiro[4,5]decane -2,4,8-trione CAS: 4-methoxycyclohexanone

~hotolisis water: 11.3 Aerobic waterlsed.: 

### - Aerobic soil: c4 0.5 Aerobic outdoor: Anaerobic soil: *--CH,

# FI 0

H

Field soil: 301.35 

# 1 Soil photolysis: CAS:Cyclohexanecarboxylic acid



# I ~~drol~sis: Photolysiswater: 28'17 Aerobic soil: Aerobic outdoor: Anaerobic Field soil: soil:
Soil photolysis: 10.0 Hydrolysis: Photolysis water: 17.5 Aerobic waterlsed.: 

### - Aerobic soil: Aerobic outdoor:

73'21 Anaerobic soil: Field soil: Soil photolysis: Hydrolysis:

Spirotetramatphoto-cyclopentyl IUPAC: (ls,&)-8'-hydroxy-4-methoxy5'-methyl-P'Hspiro[c~clohexane1 ,l '-indeno[l,2- clpyrroll-3'(8'H)-one 299.4 

### CH, H Aerobic waterlsed.: 

### - Aerobic soil: Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysiswater: 42.9' Aerobic waterlsed.: 

### -IUPAC: ethyl 2-[(5~,8~)-8-methoxySpirotetramat- 2-0x0-1- photo-2- azaspiro[4.5]dec-3- 373.4 methylcarbonate en-3-yl]-4- methylbenzyl

carbonate

IUPAC: (5~,8s)-3-[2- Spirotetramat- (h~drox~"'eth~')dphoto-Phydroxy- methylphenyll-8- 301.4 methoxy-1 

### - methyl azaspiro[4.5]dec-3- en-Pone

IUPAC: 2-[(5~,8~)-8-

methoxy-2-0x0-1- 'pirotetramat- -spiro[4.5]dec-3- 299.4 photo-2-formyl ~11-4- methylbenzaldehyde

I I I
a Not applicable owing to distinct storage instabilityof spirotetramat-enol (degradingto spirot

Spirotetramatenol-dimer 2d Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysiswater: 19.3' Aerobic waterlsed.: 

### - Aerobic soil: Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysiswater: 22.9' Aerobic waterlsed.: 

### - Aerobic soil: Aerobic outdoor: Anaerobic soil: Field soil: Soil photolysis: Hydrolysis: Photolysis water: 11.5' Aerobic waterlsed.: 

### -

Not available Aerobic soil: 5.0 Aerobic outdoor: 1.5 Anaerobic soil: 7.0 Field soil: < 0.2 Soil photolysis: 2.3 Hydrolysis: Photolysis water: Aerobic waterlsed.: 

### - 

# kfl Aerobic soil: 3.6 Aerobic outdoor: 0.9 Anaerobic soil: 4.6 Field soil: < 0.2 Photolysis water: Soil photolysis: Hydrolysis: Aerobic waterlsed.: 

### - nat-ketohydroxy during frozen 600

storage). In an outdoor metabolism study, conducted with the formulation on baresoil including naturalsunlight, dimethyl-benzoic acid was shown not to exceed 3.3 % of AR. Photo-rearrangement products produced in sterile buffer solution. Possible artifacts owingto hot-spot application in the laboratory; formation under environmental conditions (formulated a.i.) was low.

### Monitoring Datamxp Concern

No/No

No/No

No/No

Norno

NoIYes 

### StudyType

Soil Column Leaching Terrestrial Field Dissipation Aerobic Soil Metabolism Outdoor Metabolism Aerob Soil Spirotet-en01 Anaerobic Soil Metabolism Aerobic Aquatic Metabolism Soil Column Leaching Terrestrial Field Dissipation Anaerobic Soil Metabolism Aerobic Aquatic Metabolism

Aerobic SoilMetabolism Aerob Soil Spirotet-en01

Aerobic Soil Metabolism Aerob Soil Spirotet-en01 Aerobic Aquatic Metabolism

SoilPhotolysis (suppl. study) 

### Spirotetramat Degradation Products %

### ofApplied atStudy Termination

11.2 (5 days) Not available due to instability 1.1 (50 d) 1.0-2.8 (127 d) 0.1-0.9 (119 d) 7.2 (180 d, ave of two samples) <LOQ (120 d, entire system) 7.5 (5 days) <LOD (120-542 d) 2.7 (180 d, ave of two samples) <LOQ (120 d, entire system)

1.6-2.3 (50 d, for additnal samples) 1.0-1.8 (119 d)

0.4 d (14 d) 2.3-6.0 (120 d, entire system)

21.8 (7 d, ave oftwo samples) 

### Table4. 

### Maximum Degradate

SpirotetramatMA-amide

Spirotetramatdi-hydroxy

Spirotetramatdesmethyl-en01

Spirotetramat0x0-en01

Dimethyl-benzoic 

### MRID or source

OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour

OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex 

### B. Spirotetramat. B.8 Fate and Behaviour OECD 

### Reported

### Amounts of Maximum %

### of ~~~likd

11.2 (5 days) Not available due to instability 6.4 (179 d, ave of two samples) 6.2 (28 d) 5.2 (4 d) 7.2 (180 d, ave of two samples) 9.2 (60 d, entire system) 7.5 (5 days) 4.5 (14 d) 3.2 (90 d, ave of two samples) 9.8 (9 1 d, entire system)

3.8 (179 d, ave two samples) 2.0 (4 d)

2.7 (7 d) 1.1 (observed) 6.0 (120 d, entire system)

21.8 (7 d, ave of two samples)

### Monitoring 

### Data/Exp Concern

NoINo

NoIYes

Nones

NoINo 

### MRID or source

Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetrarnat. B.8 Fate and Behaviou 

# '
Study Type

OutdoorMetabolism

Soil Photolysis (suppl. study) OutdoorMetabolism

Aq. PhotolysisNatural Water Soil Photolysis (suppl, study)

Aq. Photolysis Natural Water

Hydrolysis 

# able 4. ~a&mum Degradate

acid

Spirotetramatglyoxylic amide

Methoxycyclohexanone

Methoxycyclohexylaminocarboxylic acid

Spirotetramat0x0-ketohydroxy 

### Reported Amounts of Maximum % 

### ofApplied

3.3 (7 d)

4.1 (2 d, ave of two samples) 2.3 (7 d)

17.5 (8 d) 10.0 (2 d, ave of two samples)

11.3 (10 d)

1<0.5 (observed) 

### Spirotetramat Degradationproducts %

### of

### Applied 

### at Study Termination

0.3-0.5 (127 d)

1.1-3.4 (7 d, ave of two samples) <LOQ (127 d)

16.0 (10 d) 6.1 (7 d, ave of two samples)

11.3 (10 d)



### - - -

### Monitoring DataIExp Concern Noffossible

NoIPossible

NoIPossible

NoIPossible

NO/NO~ 

### MJUD or source

OECD Monograph Annex B. Spirotetrarnat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour

- OECD Monograph Annex B. Spirotetramat. B.8 Fate and 

### Table 4. 

### Maximum Degradate

Spirotetramatphoto-cyclopentyl

Spirotetramatphoto-2- methylcarbonate

Spirotetramatphoto-2-hydroxymethyl

Spirotetramatphoto-2-formyl

Spirotetramatenol-dimer 

### 1 

### SpirotetramatDegradationProducts %

### ofApplied at Study Terniiitation

39.2 (7 d, ave two radiolabels; 35.4-42.9 for individual radiolabels)

17.7 (7 d, ave of two labels)

14.7 (7 d, ave of two labels)

5.3 (7 d, ave. oftwo labels)

0.0-0.8 (7 d, ave. two samples)
0.5 (360 d, ave of two samples) <LOQ (127 d) 1.0-3.7 (1 19 d) 

### Reported Amounts of Maximam %

### ofApplied

-

39.2 (7 d, ave two radiolabels)

19.3 (6 d, ave of two labels)

22.9 (6 d, ave of two labels)

11.5 (3 d, ave. oftwo labels)

1.9 (2 d, ave. two samples;2.3 for an individual sample) 12.7 

### (7 d) 1.5 (28 d) 5.0 (60 d) 

# '
Study Type

Aqueous Photolysis

Aqueous Photolysis

Aqueous Photolysis

Aqueous Photolysis

-- Soil Photolysis (suppl. study)
Aerobic Soil Metabolism Outdoor Metabolism Aerob Soil Spirotet-en01

### Table 4. 

### Maximum ReportedAmounts of Spirotetramat Degradation Products

~~~1e~$~~~,o~~@~e~fica17:qnd;d@ate 

### ~i~amete1:s*of~SphO:t;etramat andi~eg'1adati0.n 'Rsod%i(L"~t"s De@cte&b~SubJnitted EnvironmentalRate-&xidies Monitoring DatalExp Concern

NO/NO~

Major degradates and maximum amounts >lo% are in bold. Unacceptabledata were not reported. Refer to Table 1 for chemical names and structures. Considered as artifacts owing to hot-spot application 

### in the laboratory, formationunder environmental conditions (w. formulated a.i.) was negligible. 

### MlUD or source

Behaviour

OECD Monograph Annex B. Spirotetramat. B.8 Fate and Behaviour

ad- " ' 

### ~od&he@iical agd~&$&Para~eiers Melting point = 142°C Boiling point =

### NA, decompositionat 235OC

Solubility in organic solvents at 20°C 

### Soliient 

# I Solutiility

## &a) Ethanol 44 

### - -7.: 

# - k. A, r , 4$ s* 

## ,wade$$):

+ 

### Parent spirotetramat

IUPAC: cis-3-(2,5- 

### dimethylpheny1)-8-methoxy-2- 0x0- 1 

### -azaspiro[4.5]dec-3-en-4-y1 ethyl carbonate CAhde,:Carbonic acid, cis-3-(2,5-



### dimethylpheny1)-8-methoxy-2- 0x0-

### l-azaspiro[4.5]dec-3-en-4-yl ethyl ester 

### Study Type

Anaerobic SoilMetabolism Soil Column Leaching Terrestrial Field Dissipation Aerobic Soil Metabolism Outdoor Metabolism Aerob Soil Spirotet-en01 Anaerobic Soil Metabolism Soil Column Leaching Terrestrial Field Dissipation

A\ " " T$- 

### stru~tufk?"~* 

# ~ %

### of Applied at Study Termination

0.3 (180 d, ave of two samples) 13.7 (5 days)

0.8 (360 d, ave oftwo samples) <LOQ (127 d) 1.2-3.3 (1 19 d) 4.6 (180 d, ave of two samples) 10.8 (5 days) 

### Degradate

Spirotetramatenol-dimer 2 

### Maximum % 

### ofApplied

7.0 (6 d, ave two samples) 13.7 (5 days) <0.2 9.2 (30 d) 0.9 (7 d) 3.6 (14 d) 4.6 (180 d, ave of two samples) 10.8 (5 days) <0.2Dissociation constantpK, = 

### 5.2
Estimated Koc values from the soil column leaching studv. For spirotetramat-en01 from the column experiments: Arithmetic mean Koc

= 55 

### Llkg (mobile). AdsIDes of transformation product: two SL's, two Sics,and L. No definitive test data regarding the adsorption/desorptioncharacteristicsIUPAC: 2 cis-1-[[(2,5- 

### Dimethylphenyl)hydroxyacetyl]

log Koc obtained by HPLC method:

IUPAC or CAS name not log Koc obtained by HPLC method: pH6.0 logKoc =3.49; Koc ~3115pH 4, 20°C, ave. oftwo labels 

### Name: Spirotetramat-en01 pH 7,25"C, ave. of two labels
CAS 

### name: cis-3-(2,5-Transformation Product 2:
Name: Spirotetramatketohydroxy labels, entire system) 99.0 (7 d, ave two labels, entire system

Amount in soil (%) 10.2 9.6 11.6 17.9 labels, entire system) <LOQ (120 d, ave of two labels, entire system) Amount in leachates (%) 2.8 1.3 2.7 0.1 163-1

NA owing to distinct storage instability of spirotetramat-enol,degrading to spirotetramat-ketohydroxy during fi-eeze storage stability. 164-1

161-3

162-1 20.9 (2 d, ave 2 samples) 14.2 (126 d) 16.3 (1 d) 15.0 (1 d) 14.7 (0.25 d) aquatic metabolism

Soil column leaching

12.4-16.7 (7 d, ave two samples) 13.6 (360 d) 5.9 (50 d) 5.6 (50 d) 6.0 (50 d) Loamy sand, water pH 7.16

Totals 5 DAT Sandy loam Loam Silt loam FL sandy loam The study was conducted with spirotetramat-enol. Terrestrial field dissipation

Soil photolysis Aerobic soil metabolism 

### NY loamy sand FL sand FLsand; Cropped CA sandy loam CA SL; Cropped WA sandy loam WA loamy sand; Cropped Supplemental study, useful to identify possible photolysates. A fine sandy loam and a loam. FL sandy loam Sandy loam Silt loam Silt 

# -:AS 

### name: cis-3-(2,s- 

### )imethylphenyl)-3-hydroxy-8- nethoxy-1-azaspiro[4.5]decan- !,4-dione 162-1 Aerobic soil FL sandy loam metabolism of Sandy loam spirotetramat- Silt loam en01 Silt Non- Outdoor Loam guideline metabolism FL sandy loam study 162-2 Anaerobic Sandy loam soil metabolism 162-4 Aerobic Loam, water pH 6.8 aquatic metabolism Loamy sand, water pH 7.16 19.3 (1 d, ave. two 7.7 (180 d, ave. two values, entire values, entire system) system) 40.5 (120 d, ave two 40.5 (120 d, ave two labels, entire system) labels, entire system) 27.5 (60 d, ave two 25.4 (120 d, ave two labels, entire system); labels, entire system) [50.8 (60 d) for one label] Amount in soil (%) 8.4 3.3 6.7 11.0 Amount in leachates (%) 2.9 7.5 2.0 0.2 163-1 Soil column leaching Totals 5 DAT Sandy loam Loam Silt loam FL sandy loam The study was conducted with spirotetramat-enol.

### Name: Spirotetramat-MA-amide NA owing to distinct storage instabilityof spirotetramat-enol, degrading to 

### spirotetramat-ketohydroxy during freeze storage stability.

IUPAC 

### name: 2 cis-1-[[(2,5- Dimethylphenyl)hydroxyacetyl] amino] -4- methoxycyclohexanecarboxylic acid 164-1

7.2 (180 d, ave. two values, entire system) 2.2 (9 d, ave two labels, entire system) 8.7 (60 d, ave two labels, entire system) 9.2 (60 d for one 6.2 (360 d) 3.1 (50 d) 3.3 (50 d) 1.1 (50 d) 0.9 (1 19 d) 0.1 (119 d) 0.2 (1 19 d) 0.1 (90 d) 2.8 (128 d) 1.0 (128 d)

7.2 (180 d, ave. two values, entire system) 162-1

162-1

Nonguideline study 162-2

<LOQ (120 d, ave two labels, entire system) 1.0 (120 d, ave two labels, entire system) Terrestrial field dissipation

Aerobic soil metabolism

Aerobic soil metabolism ofspirotetramaten01 Outdoor metabolism

162-4 

### NY loamy sand FL sand FL sand; Cropped CA sandy loam CA SL; Cropped WA sandy loam WA loamy sand; Cropped FL sandy loam Sandy loam Silt loam Silt FL sandy loam Sandy loam Silt loam Silt Loam FL sandy loam

Anaerobic soil metabolism Aerobic Sandyloam

Loam, water pH 6.8 aquatic metabolism Loamy sand, water pH 7.16IUPAC name: (5s,8s)-3-(2,5- 

### dimethylpheny1)-3,4-dihydroxy-8- methoxy-1-azaspiro[4.5]decan-2-

Transformation Product 5:
Name: Spirotetramat-desmethyl-.TransformationProduct 6:
Name: Spirotetramat-0x0-en01
IUPAC name: 

### 3-(2,5- 

### dimethylpheny1)-4-hydroxy-1- azaspiro[4.5]dec-3-ene-2,8-dione

### Yame: Spirotetramat-oxocetohydroxy 

### [UPAC

### name: 3-(2,5- 

### 1imethylphenyl)-3-hydroxy- 1

### - tzaspir0[4,5]decane-2,4,8-trione

### Transformation Product 12:


### Name: Spirotetramat-photo

### IUPAC name: (1~~4s)-8'-hydroxy-4-methoxy-5'-methyl2'H-spiro[cyclohexane-l ,

### 1'- indeno[l,2-clpyrroll-3'(8'H)-one

### Transformation Product 13:
Name: Spirotetramat-photo-2- methylcarbonate
IUPAC 

### name: ethyl 2-[(5sY8s)-8-methoxy-2-oxo-l

### azaspiro[4.5]dec-3-en-3-y1]-4- methylbenzyl carbonate 

### 18.3 (6 d, ave two labels); 

### 19.3 (6 d for one radiolabel) 

### 17.7 (7 d, ave two labels) Aqueous photolysis at pH 5 rest temperature: 25OC.0.9 (7 d) 0.3 (63 d) Non- Outdoor 

# -f"I 0.9 (7 d) <LOQ (127 d) guideline metabolism 

## ."-.

<- study 4.6 (180 d) 4.7 (180 d) 162-2 Anaerobic soil

PU metabolism 2(-2H) Amount in soil ('33) Amount in leachates (%) 163-1 Soil column 4.8 NA leaching 5.9 NA 6.1 NA 10.8 NA
164-1 Terrestrial field dissipation

-- NA =Not analyzed. Loam FL sandy loam Sandyloam

Totals 5 DAT Sandy loam Loam Silt loam FL sandy loam The study was conductedwith spirotetramat-enol. NY loamy sand FL sand 1 FL sand; Cropped

I CA sandy loam

CA SL; Cropped WA sandy loam

ND =Not detected. Major degradates and maximum amounts 110%are in bold. Unacceptabledata were not reported.