### UNITED STATES ENVIRONMENT AL PROTECTION AGENCY WASHINGTON

, D

. C

. 20460

August 11. 20 1 5 OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION

MEMORANDUM 

### PC Codes : 00070 I DP B arc od e: D427577

SUB JE CT:

FROM :



### REVIEWE D BY:

T HROU G H :

TO: 

### Re gis trat i on R eview: Pr e limin ary Problem Formula ti o n for E nvironmental Fate, Eco l ogical Risk

, Endangered Species, and Human H ea lth Drinkin g Water Expos ur e Assessments for Acrolein

C hu ck Peck Environmental Engineer ,,-)")

,,, /?.... 2o i s

. 08

. 11 08 : 15:55

· L-b':-JL**~** · 04"00' 

### Thomas Steeger. Ph.D.

, Senior Science Advi so r rnoMAssmGeR ::-;:-:_-::":=- 

### Environme nt al Ri sk Branch I V

- · - -- Environmental Fate and Effects Di vision (7507P)

Jame s Breithaupt. Agronom i s t Bill Erickson. Biologist Ri sk Assessment and Science Support Branch ( RAS B ) Antimicrobials Division (7 51 O P )

CA THERINE AUBEE 

### Cather in e Aubee Senior Scientist 2015

· 08

· 11

## ~ • ..i.. ·A- ' '00'04·09:44:07 '-"!{"""-- 

### Jame s N. Car leton

. Ph.D

.. Senior Fate Scientist 

### JAMES CARLETON Katrina Whit e. Ph.D

.. Ri sk Assessment Proces s Leader E nvironmental Risk Branch IV Katrina White**0'9(..t)~t.-,J.U4.\0.lilHOfrt** ow**ta4h~l ~-...** **-w•"'--~ 1"1** **,tl'** .. lof.,,..s
CNUION**~1#~1.Ct Orf"~H0.11100:** **•** Oot'OC'



### E nvironmental Fate and E ffect s Divi s ion (7507P) 

### 2015.08. 11 09:32:09 -04'00'

Jean Holm es, D

. V.M

.. M .P.H

. Branch Chief 

# 0,,,,,,,,**-~ ~**  Enviro nm enta l Risk Bran ch I V /"""--- Environmental Fate and Effect s Division (7507 P )

Laura Par so ns. Associate Branch Chief Ri sk Assessment and Science Support Branch ( RA SSB) Antimicrobials Divi s ion (75 JOP )

Kelly Ballard. Chemical R eview Manager Tom Moriarty. Team Leader Neil Anderson

. Branch Chief Ri sk Management and Implem entation Bran ch I Pe s t icide R e -e valua tion Di v i sio n (750 8P)

Page I 

### of 43 

# t://11 It

### Page 2 of 43 1. Executive summary

The Environmental Fate and Effects Division (EFED) and Antimicrobial Division (AD) ha ve completed the preliminary problem formulation for the ecological risk, environmental fate, endangered species, and drinking water assessments to be conducted as par t of the R egistration R eview of acrolein ( 2

- propenal ; C AS No. 107

- 02

- 8; PC C ode 000701 )

. The Registration Review co nsiders existing uses for a crolein, which include use via direct application to water for aquatic plant control , applications to control bacteria and fungi in oilfield water injection systems, and applications to remove hydrogen sulfide in oilfield operations

. The environmental fate properties and use patterns of acrolein indicate that direct application of acrolein to waterways and application of trea ted water to land represent potential routes of acrolein exposure to non

target aquatic and terrestrial organisms

This problem formulation describes the methods planned to be used during the completion of drinking water and ecological risk assessments in support of Registration Review

, and provides an overview of the environmental fate, ecological effects, and potential ri sks associa ted with the use of acrolein as well as uncertainties unique to the risk assessment of acrolein . This document also identifies additional studies that would address uncertainties in assessing ecological risk ass ociated with current uses of a crolein

. The fate database is incomplete based on the environmental fate data requirements outlined in the Code of Federal Regulations Title 40 Part 158 (40CFR158) Subpart N 1 

### and data are needed to complete and reduce uncertainty in risk assessments. Additional data on the following fate parameters are recommended.

o Aerobic and anaerobic aquatic metabolism data (OCSPP 2 

### Guideline 835.4300 and 835.4400 ). The sampling intervals in the submitted studies were insufficient to estimate the degradation rate and half

- life of acrolein and 3

- hydroxpropanal in water. Draft reports for these studies are expected in Dec ember 2015. In the absence of acceptable stud ies , EFED will use the second sampling period from the available data as conservative estimates for half

- lives.

o Leaching Study (OCSPP Guideline 835.1240). As irrigation water treated with acrolein is applied
to crop

- bearing or fallow fields to be held for a period of 6 days prior to release, it is important to understand if the acrolein or its degradates will leach into groundwater underlying the fields. A previous sorption/desorption study was classified as una cceptable and a new study was required as part of the RED. A footnote for this study in the Data Call

- In Response indicated the following: Adsorption and desorption using a batch equilibrium method is preferred. However in some cases, for example, where t he pesticide degrades rapidly, soil column leaching with unaged or aged columns may be more appropriate to fully characterize the potential mobility of the parent compound and major transformation products . Subsequently, the registrant submitted a protoco l for a soil leaching study (OCSPP 835.1240), which was reviewed by EFED in 2011 but the required data have not been submitted to date. A draft report for this study is expected in December 2015. In the absence of data, EFED will estimate K oc 

### using EPISu ite.

o Aerobic soil metabolism data (OSCPP Guideline 835.4100). N o acceptable aerobic soil metabolism data are available. In 2011, EFED granted the registrant a waiver for these data (DP Barcode 386809, February 2011), indicating the following:

In March 2007 EFED reviewed the submission of four studies pertaining to soil and aquatic metabolism (DP Barcode D334823). In the cover memorandum, EFED stated “Note that the two soil metabolism studies {an aerobic soil metabolism study (MRID 43037301) an d anaerobic soil metabolism study (MRID 43035701)} are not required to support the current use patterns, aquatic

non

- food and indoor, for acrolein, but would provide useful information if available as irrigation

1 CFR. 2013. Title 40 (Protection of the Environment), Cha p ter 1 (Environmental Protection Agency), Subchapter E (Pesticide Programs), Part 158 (Data Requirements for Pesticides), Subpart N (Environmental Fate) http://www.ecfr.gov/cgi

- bin/text

idx?c=ecfr&SID=ff5c7fef3645e7cd5abceca0b597bccb&tpl=/ecfrbrowse/Title40/40cfr158_main_02.tpl
2 The Series 835 Fate Guidel ines were completed when the Office of Chemical Safety and Pollution Prevention (OCSPP) was known as the Office of Prevention, Pesticides, and Toxic Substances (OPPTS)

.

### Page 3 of 43 water containing acrolein is routinely appli ed to agricultural fields.” According to 40 CFR 158.1300, aerobic soil metabolism (835.4100) and anaerobic soil metabolism studies (835.4200) are not required for applications to aquatic environments and indoor uses. As such, EFED recommends that the requ ested waiver for the aerobic soil metabolism and anaerobic soil metabolism studies requirement be granted.

However, given that the irrigation water can be applied to agricultural fields, there is the potential for terrestrial exposure. Additionally, impa cts on groundwater will also be evaluated and the data would provide useful information on the degradation rate of acrolein prior to entering the groundwater. In the absence of an acceptable study, EFED will assume acrolein is stable to aerobic soil metab olism

. The ecological database is also incomplete based on the ecological effects data requirements outlined in the 40CFR158 Subpart G 3



### . Additional toxicity data on the following taxa are recommended for the irrigation water use of acrolein

. No additional data are needed for the oilfield use.

Avian dietary toxicity test ( OCSPP 850.2200 4 

### ). Birds ( e.g ., water fowl) may f orage on plants i n treated water and a broader range of birds may forage in agricultural fields/rangeland where acrolein

t reated waters may be applied with the intent of dissipating the compound ; therefore, residue ingestion is a potential route of exposure to birds . Currently, no subacute dietary toxicity data are available for birds.

Tier 2 Seedling emergence and seedl ing growth (OCSPP Guidelines 850.4100 5 

### ) and vegetative vigor (850.4150 6 

### ) studies were provided subsequent to publication of t he RED on acrolein (USEPA 2008 a 7 

### ) ; however, these data do not adequately address the uncertainty regarding the potential effects of applying the maximum estimated rate of acrolein

- treated irrigation water to terrestrial plants as both studies did not establish a definitive no adverse effe ct concentration (NOAEC) for some of the plant species tested nor did the test establish an effect concentration at which 25% of the tested plants exhibit effect, i.e ., EC 25 

### . The maximum application rate tested in the earlier studies was less than the est imated rate (0.54 lbs a

. i

. /A) applied to agricultural fields and rangeland in order to dissipate the compound.

Pollinator toxicity data consisting of an acute contact test with adult honey bee s (850.3020; OECD 214), acute oral test with adult honey bee s (OECD 213 ), acute honey bee larvae test (OECD 237), 10

- day adult honey bee test (draft OECD guideline) and the 21

- day larval honey bee toxicity test (draft OECD guidance) are needed since the current label allows for application to rangeland or to crops that may be in bloom, in which case bees may be exposed. Pending the outcome of the lower

tier laboratory

- based acute and chronic toxicity studies of individual adult and larval honey bees, higher

- tier studies, i.e ., semi

- field (OECD 75; 850.303 0) and full

- field (850.3040) may be required Appendix C provides rationales for the pollinator

- related data.

3 CFR. 2013. Title 40 (Protection of the Environment), Chapter 1 (Environmental Protect ion Agency), Subchapter E (Pesticide Programs), Part 158 (Data Requirements for Pesticides), Subpart G (Ecological Effects) http://www.ecfr.gov/cgi

- bin/text

idx?c=ecfr&SID=ff5c7fef3645e7cd5abceca0b597bccb&rgn=div6&view=text&node=40:25.0.1.1.9.7&idno=40

4 USEPA. 2012. Ecological Effects Test Guidelines. OCSPP 850.2200: Avian Dietary Toxicity Test. . Office of Chemical Safety and Pollution Prevention (7101) EPA 712

- C

- 024. January 2012. http://www.regulations.gov/#!documentDetail;D=EPA

- HQ

- OPPT

- 2009

- 0154

- 0011

5 USEPA. 2012. Ecological Effects Test Guidelines. OCSPP 850.4100: Seedling Emergence and Seedling Growth. Office of Chemic al Safety and Pollution Prevention (7101) EPA 712

- C

- 012. January 2012. http://www.regulations.gov/#!documentDetail;D=EPA

- HQ

- OPPT

- 2009

- 0154

- 0023

6 USEPA. 2012. Ecological Effects Test Guidelines. OCSPP 850.4150. Vegetative Vigor. Office of Chemical Safety and Pollutio n Prevention (7101) . EPA 712

- C

- 011. January 2012. http://www.regulations.gov/#!documentDetail;D=EPA

- HQ

- OPPT

- 2009

- 0154

- 0024

7 Ibid USEPA 2008a.

### Page 4 of 43 2. Introduction

A crolein is a reactive aldehyde and is considered a contact herbicide that is phytotoxic to most submerged aquatic vegetation. Acco rding to the product data fact sheet for MAGNACIDE ® 

### H Herbicide, acrolein is a general cell toxicant which reacts with sulfhydryl groups in proteins. In a review of acrolein toxicity, Beauchamp et al

. 8 

### attributed the toxicity of acrolein to the chemical’s reaction with critical sulfhydryl groups present in proteins and peptides that play important roles in chemical reactions of living cells. Submerged aquatic plants treated with MAGNACIDE ® 

### H Herbicide a re intended to gradually disintegrate into small fragments and float downstream.

EFED evaluated the most recent ecological risk assessment s for acrolein in association with any available updated toxicity, exposure, and usage information to determine if su fficient data are available or if further updates are needed to support Registration Review

. R ecent risk assessment s include the 20 08 EFED ecological risk assessment of a crolein in support of the reregistration eligibility decision (RED ; USEPA 2007 9 

### ) and the 2011 assessment of the potential risks to the Federally t hreatened Alameda w hipsnake ( Masticophis lateralis euryxanthus ) in California (USEPA 2011 10 

### )

. AD has not previously evaluated ecological risks from anti microbial use of acrolein in oilfield wells, but the exposure is expected to be minimal and therefore ecological risks are not anticipated for this use (see Section 7b for further discussion). No new uses have been assessed since that time. EFED and AD h a ve also considered the latest Agency science policies and risk assessment methodologies in compiling this problem formulation

.
3. Use Characterization

Acrolein is marketed by Baker Petrolite Corporation (BPC) and is the active ingredient in MAGNACIDE ® 

### H Herbicide (EPA Registration Number 10707

- 9), a restricted use pesticide for control of submerged and floating aquatic weeds and algae in irrigation canals and irriga tion reservoirs in some states. 11 

### The chemical was first registered as a n herbicide in 19 75 by BPC, but was previously registered in 1959 by Shell as Aqualin (92% active); however, this formulation is no longer supported

.
When used as a herbicide, a crolein is applied directly under the water’s surface through a closed delivery system ( i.e
., steel cylinders designed to prevent applicator exposure )

. P roducts are supplied in pressurized containers where nitrogen is used to force the liquid chemical out of the container through a metering device. It is then injected directly below the surface of moving water in the canal where it is carried along by the flow

. Applications are made to a treatment area at a desired treatment concentration for specific periods of time depending on the extent of aquatic plant growth conditions. Use of acrolein is ty pically limited to arid western states where crops are irrigated. The label stipulate s the following: “ Do not use where waters will flow into potential sources of drinking water. W ater treated with [acrolein] must be used for irrigation of fields, either crop bearing, fallow, or pasture, where the treated water remains on the field OR held for 6 days before being released into fish bearing waters or where it will drain into them ”. The current label indicates that the product can be applied a maximum of ei ght (8) time s annually , with a minimum two (2) week retreatment interval per application

. The amount of acrolein required to treat the irrigation system is primarily determined by the volume of water and weed density, although water velocity, temperature and quality must also be considered. E ffective treatment concentrations in irrigation systems are as high as 15 mg/L, with application times (exposure periods) ranging from 30 minutes to 8 hours (see label for more details)

.

8 Beauchamp, R. O. Jr., D. A. Andj elkovich, A. D. Kligerman, K. T. Morgan, and H. d’A. Heck 1985. A Critical Review of the Literature on Acrolein Toxicity. CRC Critical Reviews in Toxicology 14: 309

– 380.

9 USEP A 2008 . Environmental Fate and Ecological Risk Assessment Chapter (DP Barcode D354775) n Support of Phase VI of the Reregistration Eligibility Decision on Acrolein (PC Code 000701).

10 USEPA 2011. Risks of Acrolein Use to Federally Threatened Alameda Whipsnake ( Masticophis lateralis euryxanthus ) Pesticide Effects Determinations, Environmental Fate and Effects Division, Office of Pesticide Programs, Washington D.C. 20460. September 16, 2011.
11 Baker Petrolite. 2000. MAGNACIDE ® H Herbicide Product Data.

### Page 5 of 43 A crolein is also the active i ngredient in restricted use broad

- spectrum microbiocides used to control bacteria and fungi in oilfield water injection systems and to remove hydrogen sulfide in oilfield operations (MAGNACIDE ® 

### B ; EPA Registration Number 10707

- 10 ; and

, AcroCide TM 

### ; EPA Registration Number 71173

- 1) . In addition to its use as a pesticide, acrolein is primarily used as an intermediate in the manufacture of plastics; it is also used in manufacturing perfumes, pharmaceuticals, and animal feed additives (USEPA 2008 a ) . Oth er sources of acrolein in the environment include its formation from the breakdown of certain pollutants in outdoor air or from burning tobacco or gasoline. The most recent version of the Toxic Release Inventory report indicates that since 2007, most of th e releases of acrolein have been to on

- site underground injection wells (maximum of 1,602,000 lbs in 2008), with releases to surface water in the United States being less than 141 lbs/year, except for in 2012 when 390 lbs were released.

Currently, there a re 3 active Section 3 registrations for acrolein and 6 Special Local Needs (SLN; Section 24c) registrations. There are no registered pesticide products that contain acrolein and other active ingredients.

The chemical profile , located in the docket, produced by the Biological and Economic Analysis Division ( BEAD ) lists the use patterns associated with active registrations of a crolein . EFED will rely on the BEAD chemical profile when estimating environmental exposure s that result from these registere d uses. Additionally, in order to be protective, EFED will utilize the use information that result s in maximum
exposure ( e.g. , concentration) estimates for a given use pattern for the drinking water and ecological risk
assessment s

. If the labels (and consequently the BEAD chemical profile) do not include all information needed to enable estimat ion of maximal exposure s , such as the maximum single treatment concentration

, minimum retreatment interval, and annual maximum treatment conce ntration allowed (lbs a.i./year), EFED will make conservative assumptions regarding these use parameters

.
4. Conclusions from Previous Risk Assessments

a. Ecological Risk Assessment

Two previous ecological risk assessments have been completed for acrolein , specifically MAGNACIDE ® 

### H : a n ecological risk assessment ( USEPA 200 8b 12 

### ) in support of the reregistration eligibility decision (RED) and a n endangered spe cies assessment for the Alameda w hipsnake in California ( USEPA 2011 13 

### ) . The uses evaluated in the risk assessments include direct application to irrigation canals and irrigation reservoirs to control aquatic weeds and algae

. Both risk assessments found potential for direct effects to listed and non

listed aq uatic and terrestrial animals and plants. Exposure pathways for aquatic organisms and plants included s urface waters contaminated with acrolein through direct application and from tre ated irrigation water that flowed into receiving rivers, streams, or lakes. E xposure pathways for terrestrial plants and animals included application of acrolein

- treated irrigation water to agricultural fields and ingestion of contaminated water and inhalation of volatilized acrolein.

T he major environmental fate and ecological risk conclusions identified in previous assessments are summarized in Table 1 and 2

.

Table 1 . Potential for direct effects identified in previous assessments for a crolein ( MAGNACIDE ® H 

### ) 1 Listed/or

non - listed Birds 2 Mammals Terrestrial Invertebrates Aquatic Vertebrates 3 Aquatic Invertebrates Terrestrial Plants Aquatic Plants Non

- listed Yes* Yes Presumed 4 Yes Yes Presumed Yes Listed Yes * Yes Not evaluated Yes Yes Presumed Yes

-- = Risk below LOC; * indicates a full data set is not available

1 Risk concerns were identified when the RQ exceeded the corresponding level of concern in a previous risk assessment or were identified as a potential concern based on weight of evidence.

12 Ibid USEPA 2008 a

. 13 Ibid USEPA 2011.

### Page 6 of 43 2 Birds serve as surrogates for terrestrial

- phase amphibians and reptiles.

3 Fish serve as surrogates for aquatic

- phase amphibians.

4 Toxicity data not a vailable, risk presumed.

Table 2 . Potential fate concerns identified in previous assessments for acrolein ( MAGNACIDE ® H 

### ) Bioconcentration/ Bioaccumulation 1 Ground w ater Contamination 2 Sediment Persistence 2 Residues of Concern Volatilization
No, log K ow <3 No No No A crolein and 3

- hydroxypropanal Yes

1 Based on whether previous assessments indicated this was a risk concern or if previous assessments ran K ow Based Aquatic Bioaccumulation Model (KABAM) for chemicals with a log K ow >3.

2 Based on data for acrolein and 3

- hydroxpronanl, which exists in equilibrium with acrolein.



### b. **Drinking Water Exposure Assessments**

The most recent drinking water assessment was a qualitative assessment completed in 20 07 ( USEPA 20 07 b )

. The residue s of concern for acrolein in terms of human health w ere acrolein and its hydration product 3

- hydroxypropanal

. It was b ased on the limited available laboratory fate data, and the available field study and monitor ing study data . W hile it appeared that acrolein dissipate d from irrig ation canals with a half

- life of less than one day, monitoring data indicated acrolein wa s sufficiently persistent and mobile such that it could reach the drainage points of irrigations systems in concentrations frequently between 0.1 and 1 mg/L (part per million; ppm ) and at distances up to 70 miles from the a pplication point. This indicated that if water containing acrolein r eached the terminus of an irrigation system, and could not be held back by containment or diversion structures, acrolein w ould enter natural waters. The concentrations at a drinking water facility downstream from a discharging irrigation system would depend upon the dilution due to the relative flow rates of the irrigation system (or volumes in the case of reservoirs) and of the receiv ing water body, and the travel time between the two points.

**c. Clean Water Act Programs** 

A crolein is not identified as a cause of impairment for any water bodies listed as impaired under section 303(d) of the Clean Water Act. 14 

### No Total Maximum Daily Loads (TMDL) or section 304(a) ambient water quality criteria have been developed for a crolein

. 15 

### Aquatic life benchmarks 16 

### have been established for acrolein ; however, a ny data submitted or otherwise located as part of the Registr ation Review process that indicate greater sensitiv ity than data currently available may be used to revise aquatic life benchmarks if applicable.

5. Environmental Fate and Transport

Acrolein is a highly reactive molecule with other chemicals because both the double bond and aldehydic moieties participate in many reactions (Etzkorn, 2009). It must be stabilized with hydroquinone, or it will exothermically self

- polymerize in the presence of air and ultra

- violet light, or temperatures higher than 150oC ( Ghi larducci and Tjeerdema, 1985 ). Acrolein is a liquid at 25 oC but has a vapor pressure of 0.354 atm at the same temperature (Smith 1962 ), and will rapidly volatilize if not kept in a closed container ( Ghilarducci and Tjeerdema, 1985 ). Acrolein is also very soluble in water, at 237.6 g/L at 25°C (MRID 40840602). This high solubility tends to offset the compound’s tendency to volatilize somewhat, as indicated

14 Specific state causes of impairment that make up the national pesticides cause of impairment group are listed at http://iaspub.epa.gov/tmdl_waters10/attains_nation_cy.cause_detail_303d?p_cause_group_id=885

. 15 Specific state pollutants that make up the Nat ional Pesticides Pollutant Group and have TMDLs are listed at http://iaspub.epa.gov/tmdl_waters10/attains_nation.tmdl_pollutant_detail?p_pollutant_group_id=885&p_pollutant_ gr oup_name=PESTICIDES

. 16 Aquatic Life Benchmarks are available at ( http://www.epa.gov/oppefed1/ecorisk_ders/aquatic_life_benchmark.htm

.

### Page 7 of 43 by the measured Henry’s constant of 1.9 x 10

- 4 

### atm·m3 / mol ( MRID 47008401; Salma, 2001; Smith, 1962 ). Acceptable aquatic field dissipation studies are not available for acrolein. A selection of environmental fate and transport properties of acrolein is summarized in Table 3

.

Table 3

. Chemical Properties and Environmental Fate Parameters of Acrolein
Parameter Value Description/Comments Source Selected Physical/Chemical Parameters

PC Code 0 00701

-- -- Molecular Mass 56.06 g/mol

-- -- Molecular Formula C 3 H 4 O

-- -- Vapor pressure (2 5 o C) 269 torr Intermediate to high volatility under field conditions Smith 1962

Aqueous solubility ( 2 5 o C) 237.6 g/L MRID 408406

- 02

H enry’s Law Constant 1.95 x 10

- 4 atm

- m 3 /mol E xpected to volatilize from water or moist/wet soil surfaces. MRID 470084

- 01

Log octanol

- to

- water partition coefficient (Log K OW ) 0.98

- 1.10 MRID 408406

- 04

Persistence 3

Hydrolysis half

- life (25 ° C) 3.8 days (pH 5.28) 1.5 day s (pH 7.19) 0.8 day s (pH 8.92) Does not hydrolyze , equilibrates with 3

- hydroxypropanal

. MRID 409454

- 01

Aqueous photolysis half

- life (20 ° C) 0. 1

- 0.3 days (pH 4 and 7 )
0. 06

- 0.2 days (pH 9 ) May photolyze in clear, shallow waters. Adjusted for sunlight intensity at 40 ° N latitude. MRID 493730

- 0 1

Soil photolysis half

life No Data

-- --

Aerobic soil metabolism half

- life No Data

-- --

Anaerobic soil metabolism half

- life No Data

-- --
Aerobic aquatic metabolism half

- life (20 ° C) <1 day < 14 days Data insufficient to estimate half

- life. For MRID 49373002, the percent of acrolein was well below 50% by the second sampling interval at 14 days. MRID 4 28376

- 01 MRID 493730

- 02

Anaerobic aquatic metabolism half

- life (20

- 26 ° C) <1 day < 14 days Data insufficient to estimate half

- life. For MRID 49373002, the percent of acrolein was well below 50% by the second sampling interval at 14 days. MRID 4 29492

- 01 MRID 493730

- 02

Mobility

Solid

- water distribution coefficient (K d ) in L/kg

- soil No Data

-- --

Fish Bioconcentration

Fish bioconcentration factors (steady

- state); depuration rate Under review

-- MRID 432252

- 01

### Page 8 of 43 Abiotic Degradation

Acrolein does not follow ideal liquid behavior, as the measured partial pressures are about twice what would be predicted from Raoult’s Law. The Henry’s Law constant (K Hen 

### ) varies according to temperature according to Equation 1 where t is temperature in degrees Celsius. This suggests that acrolein may be undergoing a reversible dimerization reaction in aqueous solution. Acrolein does form a dimer through the addition of one acrolein molecule across the double bond of a second forming 3,4

- dihydro

- 2H

- pyran

- 2

- carboxaldehyde.

KK HHHHHH 

### = 55

. 555555

− 7777 (

− tt ) Equation 1



### Acrolein does not undergo hydrolytic degradation in aqueous solution, but ra ther goes into equilibrium with a hydration product, 3

- hydroxypropanal, in which water has added to the double bond (MRID 40945401). The observed rate of reaction varies with pH, with half

- lives of 92, 37, and 19 hours at pH values of 5.28, 7.19 and 8.92, respectively. Aqueous photolysis d ata suggest that acrolein breaks down rapidly in water

, with a half

- life ranging from 1.5 to 7.5 hours

. Data on the formation of degradates was not provided, as the study authors assumed that after 24 hours there was com plete conversion of the acrolein to the hydrolysis product 3

- hydroxypropanal

. Biotic Degradation

Submitted data (MRID s 42837601 and 42949201) indicate that acrolein degrade s by both aerobic and anaerobic metabolism , with an observed 50% degradation time ( DT 50 

### ) of about day ; however

, the available studies were not sufficient ( e.g. , insufficient sampling intervals) to quantify degradatio n rates

. An additional aquatic study was submitted to quantify the deg r a d a tion rate (MRID 49373002), but the sampling intervals were insufficient. Acceptable aerobic and anaerobic soil studies have not been submitted.

Sorption/Desorption

No acceptable data are available for estimating sorption coefficient ( e.g ., K d 

### ) values f or acrolein. Qualitative information can be used from the metabolism stu dies and chemical properties of acrolein to identify the potential adsorption/desorption of acrolein. In the aerobic and anaerobic aquatic metabolism studies cited above, acrolein was not identified in the sediment of the test vessels. This suggests that acrolein does not partition into sediment to any significant extent. In addition, the very high solubility (237 g/L at 25°C) would suggest a very low tendency to sorb to sediment.

Mo nitoring data

Studies conducted in Washington and Nebraska

, discussed in the paragraphs below, indicate that, while acrolein dissipate d with half

- lives of less than 1 day, it was sufficiently persistent to move long distances in surface water , up to 60 miles at concentrations up to 0.0 5 m g/L. These studies were conducted in the 1980s and were used to adjust label language to include required holding time for treated water or to use as irrigation water whereby the compound can dissipate withou t entering natural waters

. D ata collected from the early to mid

- 2000s in California ( USEPA 2008 b ) do not necessarily substantiate such a persistence trend at downstream sites , as the downstream sampling sites registered both non

- detects (detection limits around 5

- 20 μg/L) as well as concentrations in the milligrams per liter range

. EFED will search for more recent data to support or refute these conclusions.

In five of the eight canals evaluated by the State of Nebraska , acrolein was found in measurable concentrations (34

- 1,150 μg/L) just upstream from the discharge of the irrigation system. Dissipation h alf

lives were estimated for seven of the eight canals and ranged from 2 to 9.8 h.

### Page 9 of 43 In a companion study reported with the Nebraska monitoring data, acrolein dissipated below the detection limit of 10 μg/L during transit across a 0.15

- mi long irrigation ditch in a bean field. As a result of this study, the registrant recommended diversion of irrigation water into holding ponds or onto irrigated crops t o avoid discharge of irrigation water containing acrolein. Note that while the current labels recommend 6

- day or 2

- day holding times (SLN labels), depending on the State, the label states that water treated must be used for irrigation of fields or held, al though it does not indicate how the water is to be held.

In the second study in Washington State (MRID 47008404), the primary purpose of which was “to provide data to substantiate the viability of a lower, more realistic holding restriction for treated wa ter in the state of Washington.”. Treatment rates ranged from 1 to 3 mg/L. When dissipation half

- lives could be estimated they were, in general, somewhat longer than in Nebraska and rang ed from 12 to 19 h. In all cases measurable concentrations of acrolein (20

- 410 μg/L) were found in the discharge from the canals.

Baker Performance Chemicals concluded in their report that “if irrigation districts are unable to pond treated water for the required holding time, then diverting the wave of treated water onto i rrigated crops near the wasteways can be viewed as a reasonable alternative. If no weed or algae control is desired near the wasteway, the districts can also move their applications further upstream in the canals.”

An air monitoring study (MRID 47008407) was conducted by the registrant in 2005 associated with an application to the Kern Island Canal in the Kern Delta Water District in California in August, 2005. These data can be used to estimate exposure via inhalation. The application of 3.9 ppm was start ed at 7:30 in the morning and continued for 4 hours. Six air monitoring stations were set up on both banks, four on the windward side and two on the downwind side of the canal, within 150 ft of the injection point. A control air monitoring site was placed upstream and upwind of the application site. Analytical methods for the air samples were not reported. Air samples were also collected concurrently by the California Air Resources Board; the results from these samples are not available. The upwind samples on the upwind bank ranged from 28 to 36 μg/m 3 

### with the values increasing with distance downstream from the application point. The downwind samples were 92 and 120 μg/m 3 

### with the lower value parallel to the application point and the higher value 52 feet do wnstream. Because concentrations were still rising with distance downstream, it is conceivable that higher air concentration could have been seen further downstream. This would be supported by concurrent measurements of the concentration in the treated can al where concentrations increased from the application point to at least 867 feet downstream, the farthest downstream measurements were made in water. This apparent increase is likely due to incomplete mixing of acrolein in the canal.

**a. Transformation**  **Products**

Both aerobic aquatic (MRID s 42837601) and anaerobic aquatic metabolism stud ies (MRID 42949201) had evidence of both oxidation and reduction processes occurring in the test systems as both oxidative and reductive degradates of the pesticide were produced. Degradates formed include acrylic acid, propionic acid, oxalic acid , a llyl alcohol

, and carbon dioxide. Both reduction and oxidation products c ould occur in these test systems as there wa s a redox gradient between the water column and the bottom sediment, with the water column generally being relatively more oxidized than the bottom sediment. As discussed above, acrolein does not undergo hydrolytic degradation in aqueous solution, but rather goes into equilibrium with a hydration product, 3

- hydroxypropanal, in which water has added to the double bond. As such, the 3

- hydroxypropanal is not expected to be persistent, just like acrolein. The abiotic degradate 3

- hydroxypropanal was identified as a minor degradate, as well as 3

- hydroxypropioni c acid, which probably formed by oxidation of the aldehyde. Based on EPISuite analyses, 3

- hydroxpropanal is considered mobile,

### Page 10 of 43 with a K oc 

### of 1 L/kg oc 

### . Table 4 lists the degradates and the maximum percentage of the nominal parent concentrations by study t ype. The structures of degradates are provided in Table 5

.

Table 4

. Maximum percentage of the nominal concentration of degradates formed from acrolein by metabolic degradation processes. The time after experiment initiation that maximum occurred is in parentheses.

Degradate Hydrolysis Aerobic Aquatic Metabolism Anaerobic Aquatic Metabolism MRID 42837601 MRID 42837601 MRID 49373002 MRID 42949201 MRID 49373002 Acrylic acid ND 19% (2 d) 3.1% (0 d) 38% (1 d) 6.7% (14 d) Allyl alcohol ND 8% (0 d) <1.7% 17% (1 d) <1.7% Propionic acid ND 20% (2 d) <0.7% 64% (8 d) 2.2% (14 d) Oxalic acid ND 2% (2 d) 6.2% (28d) 49% (30 d) 22.7% (42 d) Bicarbonate ND 39% (5 d) NA 89% (30 d) NA 3

- hydroxypropanal 90.9%* (all pHs) ND Detected 7% (1 d) Detected 3

- hydroxypropionic acid ND 9% (2 d) NS 4% (1 d) NA Propanol ND 21% (1 d) <1.7% 9% (1 d) <1.7% Glyceric acid ND 1% (5 d) NA NA NA Malonic acid ND NA 0.9% (0 d) NA <1.7% NA

– not analyzed , ND

– not detected *estimated equilibrium concentration

Table 5

. Structures of Acrolein and Its Environmental Transformation Products Code Name/ Formula/MW/ SMILES Chemical Structure
Acrolein IUPAC: Prop

- 2

- enal CAS: 2

- Propenal CAS Number: 107

- 02

- 8 SMILES: O=CC=C PC Code : 00 07 0 1 H

H C H

H O

3

- Hydroxypropanal CAS Number: 2134

- 29

- 4 SMILES: C(=O)CCO O

O H H

Acrylic acid CAS Number: 79

- 10

- 7 SMILES: O=C(O)C=C O H O

Allyl alcohol CAS Number: 107

- 18

- 6 SMILES: OCC=C CH C H 2 O H C H 2

Propionic acid CAS number: 79

- 09

- 4 SMILES: O=C(O)CC

O O

H

Oxal ic acid CAS Number: 144

- 62

- 7 SMILES: O=C(O)C(=O)O O

O O H

O H

Malon ic acid CAS Number: 141

- 82

- 2 SMILES: O=C(O) C C(=O)O O O

O H O H

### Page 11 of 43 Code Name/ Formula/MW/ SMILES Chemical Structure

Bicarbonate CAS Number: 71

- 52

- 3 SMILES: O=C(O)O

3

- Hydroxypropionic acid CAS Number: 503

- 66

- 2 SMILES: OCCC(O)=O

Propanol CAS Number: 71

- 23

- 8 SMILES: OCCC C H 2 O H C H 2

C H 3

Glyceric acid CAS Number: 473

- 81

- 4 SMILES: OCC(O)C(O)=O



### 6. Receptors

Table s 6 and 

### 7 provide a summary of the most sensitive acute and chronic toxicity values for acrolein across aquatic and terrestrial taxonomic groups, respectively. Based on the available ecotoxicity information

, acrolein is very highly toxic to freshwater fish (which serve as surrogates for aquatic

- phase amphibians) and invertebrates, estuarine/marine invertebrates

, and to bird s and it is highly toxic to mammals and estuarine/marine fish on an acute exposure basis . Chronic exposure to acrolein resulted in reduced growth and survival in fish and reduced survival in aquatic invertebrates. Chronic exposure in mammals resulted in decreased growth in both parents and offspring. No chronic to xicity data are available for birds , which serve as surrogates for terrestrial

- phase amphibians and reptiles . Median effect concentrations for vascular and nonvascular aquatic plants are 36 and 72 μg/L, respectively. There are no guideline data available with which to evaluate the toxicity of acrolein to terrestrial plants. No toxicity data are available on 3

- hydroxypropanal



### .

**a. Effects to Aquatic Organisms** 

Table 6

. Summary of the Most Sensitive Endpoints from Aquatic Toxicity Studies for Technical Acrolein

Taxonomic

Group Study Type Surrogate Species Toxicity Value Acute Toxicity Classification Source (MRID)

Freshwater Amphibian Acute African clawed frog Xenopus laevis LC 50 = 7 μg/L Very h ighly toxic Holcombe et al. 1987*

Freshwater Fish Acute Fathead minnow ( Pimphales promelas ) 96

- hr LC 50 =14 μg a.i./L Very highly toxic Holcombe et al. 1987*

Chronic Fathead minnow ( Pimphales promelas ) NOAEC = 11.4 μg a.i./L LOAEC = 20.8 μg a.i./L NA Acc. No. 05008271

Freshwater invertebrates Acute Waterflea Daphna magna EC 50 <31 μg a.i./L Very h ighly toxic 415132

- 02

### Page 12 of 43 Taxonomic

Group Study Type Surrogate Species Toxicity Value Acute Toxicity Classification Source (MRID)

Chronic Waterflea ( Daphnia
magna ) NOAEC = 7.1 μg a.i./L LOAEC =16.9 μg a.i./L NA Accession No. 05008271

Estuarine/marine fish Acute L ongnose killifish 48

- hr LC 50 = 240 μg a.i./L Highly toxic 402284

- 01

Chronic No data

Estuarine/marine shrimp Acute Brown shrimp ( Penaeus aztecus ) 48

- h EC 50 of 100 μg a.i./L Highly toxic 402284

- 01

Estuarine/marine mollusk Acute Eastern oyster shell deposition ( Crassostrea virginica ) 96

- hr E C 50 =55 μg a.i./L Very highly toxic 402284

- 01

Estuarine/marine invertebrate Chronic No data

Aquatic plants Vascular Duckweed ( Lemna gibba ) EC 50 = 72 μg a.i./L NOAEC = 25 μg a.i./L NA 426209

- 04

Non

vascular Marine Diatom ( Skeletonema costatum ) EC 50 =28 μ g/L NOAEC = 25
μ g/L NA 426209

- 03

NA=not applicable



### b. **Effects to Terrestrial Organisms**

Table 7

. Summary of the Most Sensitive Endpoints from Terrestrial Toxicity Studies for Technical A crolein

Taxonomic

Group Acute/ Chronic Surrogate Species Toxicity Value Acute Toxicity Classification Source (MRID)

Birds (surrogate for

terrestrial

phase amphibians and reptiles) A cute Mallard duck Anas platyrhynchos LD 50 = 9.11 mg a.i./kg bw Very highly toxic 00117668

C hronic No Data

Mammals A cute Laboratory rat Rattus norvegicus LD 50 = Males: 10.3 Females: 11.8 mg/kg Highly toxic 412570

- 01

C hronic Laboratory rat Rattus norvegicus NOAEL= 3 mg/kg/day LOAEL=6 mg/kg/day NA 418691

- 01

Terrestrial invertebrates A cute Honeybee Apis mellifera No data

Terrestrial

Plants N/A Seedling Emergence Monocots NOAEL =0.074 lbs ai/A NA 486438

- 01 a

N/A Seedling Emergence Dicots NOAEC=0.074 lbs ai/A NA 486438

- 01 a

N/A Vegetative Vigor Monocots NOAEC=0.081 lbs ai/A NA 486438

- 02 a

N/A Vegetative Vigor Dicots NOAEC=0.081 lbs ai/A NA 486438

- 02 a

NA=not applicable

a studies have not completed final review.

### Page 13 of 43 **c. Ecological Incidents** 

A review on June 8

, 201 5 of the Ecological Incident Information System (EIIS, version 2.1.1), which is maintained by the Agency’s Office of Pesticide Programs, identified 14 reported incidents that may have involved exposures of acrolein between 1971 and 20 11 . Of the 14 reported incidents, 1 involv ed terrestrial plants, 12 involved effects to fish, amphibians and/or aquatic invertebrates and 1 involved effects to aquatic birds. Residue analysis was conducted to confirm the presence of acrolein in only one (B0000

- 500

- 8 7) of the re ported incidents. H alf of all the reported incidents occurred in California

, 2 occurred in Nevada , and a single incident each in Arizona, Colorado, Idaho, Oregon, and Nebraska . It is important to note that these incidents only reflect those reported to the Agency and may not reflect the total number of incidents that may be associated with exposure to acrolein through the use of this chemical as an herbicide.

Incidents inclu ded in EIIS are defined by a certainty index 17 

### associated with the likelihood that the pesticide application described resulted in the observed incident. The certainty index defines incidents as unrelated, unlikely, possible, probable and highly probable. Of the 14 reported incidents, 2 was classified as possible, 8 were classified as probable, and 4 as highly probable. Five of the incidents were attributed to misuse, 4 were undetermined, and 5 were the result of a registered used. One note of uncertainty associated with this data base is the nature of reporting of incidents. Many more incidents may have occurred due to acrolein exposures but may not have been reported due to various factors, such as a lack of reporting, or an absence of witness es

. Thus t he number and certainty of incident report s i s not necessarily an accurate indication of the true prevalence of incidents.

7. Exposure Pathways of Concern

a. Irrigation Water Use

The environmental fate properties and use patterns of a crolein indicate that direct application of acrolein to waterways and application of treated water to land represent potentia l route s of a crolein exposure to non

target aquatic and terrestrial organisms. Drinking water and inhalation exposure pathways for birds and mammals were previously evaluated in the Alameda w hipsnake assessment ( USEPA, 2011 ) based on maximum registered treatment rate ( i.e ., 15 mg/L) for the direct application of acrolein to water. Acute inhalation risk quotient ( RQ ) values exceeded the acu te risk levels of concern ( LOC ) for small (20 g), medium (350 g) and large (1580 g) birds as well as for small (15 g), medium (35 g) and large (1000 g) mammals. Based on previous assessments, w hen treated water was applied to agricultural fields with the intent of dissipating the acrolein, the estimated application r ate was 0.534 lbs a

. i

. /A. T he Screening Tool for Inhalation Risk (STIR ) was also used to evaluate inhalation exposure to terrestrial organisms when acrolein

contaminated irrigation water is applied to agricultural fields; STI R results ( Appendix B ) indicated th at the inhalation pathway is a concern (LOC exceedances are expected) for birds and mammals. Potential exposure through drinking water was evaluated through the Screening Imbibition Pro gram (SIP) , which indicated that

17 The Ecological Incident Information System (EIIS) used by EPA to store incident data relies on the following certainty indices:

• Highly Probable : (residues detected in affected organisms and other lines of evidence support cause)

• Probable : (residues were not measured or the measured residues were not sufficient to be considered toxic, but pesticide was used in close proximity and would be capable of exerting such an effect)

• Possible : multiple pesticides were used in close proximity and any of them are capable of causing such an effect.

• Unlikely: there are no measured residues and the observed effects are not consistent with those caused by pesticides

use d in the area or there was no pesticide use known in the area.

• Unrelated: effects obse rved in the incident are unrelated to pesticide use.

18 USEPA 2014. Conceptual Models for Environmental Exposure Pathways of Antimicrobial Pesticides. Office of Pesticide Programs

, Antimicrobial Division, Risk Assessment and Science Support Branch. Augus t 4, 2014. EPA

- HQ

- OPP

- 2014

- 0638. http://www.regulation.gov/#!documentDetail;D=EPA

- HQ

- OPP

- 2014

- 0638

- 0002.

### Page 14 of 43 exposure through drinking water alone is of potential concern for both birds and mammals ( Appendix B )

. SIP and STIR are described in detail at http:/ /www.epa.gov/oppefed1/models/terrestrial/index.htm

.

b. Antimicrobial Use in Oilfield Injection Water

The label s with antimicrobial uses for acrolein include MAGNACIDE ® 

### B (EPA Registration Number 10707

- 10) and AcroCide TM 

### (EPA Registration Number 71173

- 1) , which are use d in oilfield injection water. Based on the registered use of acrolein in oilfield injection water and the physical/chemical and enviro nmental fate properties in Table 3 , the Agency does not consider this use to represent a significant route of exposure to non

- target organisms . First, antimicrobials are typically diluted before discharge into water, and acrolein is degraded by organic co mpounds and bacteria within the oilfield system. Second, terrestrial oil fields typically use berms and catch basins to prevent surface runoff of oil drilling muds and wastes from oil drilling areas. As a result, the Agency is not including any conceptua l models 18 

### regarding potential risks since exposure of non

- target organisms from the oilfield use is not expected.

8. Analysis Plan

**a. Stressors of Concern** 

i. Ecological Risk Assessment

The stressors of ecological concern for terrestrial organisms are residues of acrolein and 3

- hydroxypropanal

, which exists in equilibrium with acrolein

.

ii. Drinking Water

Because acrolein is only applied to irrigation canals and irrigation reservoirs in some states , and because the label states “ Do not use where waters will flow into potential sources of drinking water. W ater treated with [acrolein] must be used for irrigation of fields, either crop bearing, fallow, or pasture, where the treated water remains on the field OR held for 6 days before being released i nto fish bearing waters or where it will drain into them ”

, a drinking water assessment that evaluates impacts to surface water will not be conducted

. However, given the applications of treated water to fields for irrigation purposes and the potential for acrolein in irrigation water to leach into groundwater, EFED will consult with HED and the available monitoring data and may conduct a (human) drinking water ex posure assessment if warranted.

**b. Measures of Exposure** 

EFED will use standard available models (identified in Table 8 ) to evaluate potential exposures to aquatic and terrestrial organisms as described at http://www.epa.gov/pesticides/science/models_db.htm

. Since the previous exposure assessments were completed, four main changes in standard procedures have been made:

1) The North American Free Trade Agreement (NAFTA) Guidance for Evaluating and Calculating Degradation Kinetics in Environmental Media ( NAFTA, 2012 ; U SEPA, 2012b ) was completed. Degradation kinetics may be recalculated consistent with the updated approach. 2) The Surface Water Concentration Calculator has replaced the older version of PR ZM/EXAMS and will be used to evaluate runoff from fields treated w ith irrigation water

.

18 USEPA 2014. Conceptual Models for Environmental Exposure Pathways of Antimicrobial Pesticides. Office of Pesticide Programs

, Antimicrobial Division, Risk Assessment and Science Support Branch. Augus t 4, 2014. EPA

- HQ

- OPP

- 2014

- 0638. http://www.regulation.gov/#!documentDetail;D=EPA

- HQ

- OPP

- 2014

- 0638

- 0002.

### Page 15 of 43 3) The Pesticide Root Zone Model

– Ground w ater (PRZM

- GW) will be used for estimating concentrations in groundwater from fields treated with irrigation water ( USEPA, 2013a )

. 4) The Pesticide in Flooded Applications Model (PFAM) will b e used for estimating concentrations in waterbodies that hold and release treated water.

The most up

- to

- date procedures and models will be used in the Registration Review exposure assessments. Nonstandard modeling procedures that may be used in the risk assessment are discussed below. In the absence of data to the contrary, the T

- REX model will employ the default 35

- day foliar dissipation half

- life value

.
Irrigation Water

EFED does not currently have a standardized methodology for determining risk to non

- target plants from applications of irrigation water where surface or groundwater has been contaminated by a pesticide applied to crops. However, EFED anticipates that an i rrigation water analysis will be conducted at the time of the risk assessment using exposure values generated from currently available models such as SWCC and PFAM for surface water or PRZM

- GW for groundwater exposures. This approach will be used to deter mine a depth (in inches) of irrigation water on a one

- acre field necessary to cause an LOC exceedance to terrestrial plants and compared with representative cultural practices to characterize the potential risk associated with this exposure scenario.

Drin king Water for Ecological Organisms

Screening

- level calculations using SIP have suggested that drinking water exposure may be significant for terrestrial organisms . This exposure pathway may be further considered at the time of the risk assessment ( Appendix B ).

Table 8

. List of the various models and the related taxa for which the models will be used.

Environment Taxa of Concern Exposure Pathway Model(s) or Pathway Link

Aquatic Fish/ Invertebrates / Plants Runoff and spray drift to water SWCC http://www.epa.gov/oppefed1/models/ water/ Direct application
to water PFAM http://www.epa.gov/oppefed1/models/ water/

Terrestrial Vertebrate Residues in/on dietary items T

- REX (dietary item) http://www.epa.gov/oppefed1/models/ terrestrial/trex/trex_v1_5_webversion. xlsm

Invertebrate Contact and ingestion of residues pollen/nectar Screening

- level exposure equations identified in Appendix B http://ww w2.epa.gov/sites/production/ files/2014

- 06/documents/pollinator_risk_assessm ent_guidance_06_19_14.pdf

Plant Runoff to plants TerrPlant (Run

- off) http://www.epa.gov/oppefed1/models/ terrestrial/index.htm#terrplant
Residues in irrigation water Results from Aquatic Models http://www.epa.gov/oppefed1/models/ water/

Human Health EDWC Vertebrate Surface Water SWCC PFAM http://www.epa.gov/oppefed1/models/ water/ Ground w ater PRZM

- GW

### Page 1 6 of 43 i. Available Monitoring Data

The Agency is aware of pesticide monitoring conducted by federal and state agencies . T his information will be considered in the assessment

, to the extent that data on acrolein are available.

**c. Measures of**  **Effect**

The most sensitive toxicity data presented in Section 6 of this problem formulation will be used to calculate risk quotients for the respective taxa. Any additional information submitted by the registrant or found in the open literature prior to conduct o f the risk assessment will also be considered. The open literature studies are identified using EPA’s ECOTOXicology database ( ECOTOX) ( USEPA, 2009a ) , which employs a literature search engine for locating chemical toxicity data for aquatic life, terrestrial plants, and wildlife. The evaluation of both sources of data that meet the Agency’s standard for inclusion in risk assessments can also provide insight i nto the direct and indirect effects of pesticides on biotic communities from loss of species that are sensitive to the chemicals, and from changes in structure and functional characteristics of the affected communities.

**9. Endangered Species Assessments** 

Consistent with the Agency’s responsibility under the Endangered Species Act (ESA), the Agency will evaluate risks to listed species from registered uses of pesticides in Registration Review . The process for evaluating potential risks to listed species is further described at http://www.epa.gov/oppfead1/endanger/litstatus/riskasses.htm

.
**10. Endocrine Disruptor Screening Program** 



### Acrolein was not i ncluded in the first group of 67 chemicals issued an order to conduct Tier 1 EDSP testing. For additional information on the EDSP, visit http://www.epa.gov/endo/

.

**11. Preliminary Identification of Data Gaps** 

a. Environmental Fate

Table 9 identifies environmental fate studies by MRID that offer data for each guideline requirement, as well as study classifications and whether or not further data are needed in order to support risk assessment.

Table 9

. Submitted Environmental Fate Data and Study Classifications for Acrolein

OCSPP Guideline Data Requirement Submitted Studies (MRID) Study Classifications Are data needed to conduct risk assessment? Justification and Assumptions EPA will Make in Absence of Data

835.2120 Hydrolysis 409454

- 01 Acceptable No

835.2240 Aqueous photolysis 409454

- 02 493730

- 01 Unacceptable Supplemental No

--

835.2410 Soil photolysis 409454

- 02 Unacceptable No Looked at soil photolysis of acrolein deposited from gas phase Not needed for modeling purposes

835.2370 Photodegradation in Air 486813

- 01 Acceptable No

### Page 17 of 43 OCSPP Guideline Data Requirement Submitted Studies (MRID) Study Classifications Are data needed to conduct risk assessment? Justification and Assumptions EPA will Make in Absence of Data

835.4100 Aerobic soil metabolism 430373

- 01 Supplemental, not upgradable Yes The estimated material balances calculated from the study were incomplete

. Data requirement waived in 2011 (DP Barcode 386809) Requesting data based on use as irrigation water

835.4200 Anaerobic soil metabolism 43035701 Unacceptable No Not needed for modeling purposes

835.4300 Aerobic aquatic metabolism 428376

- 01 432271

- 01 Supplemental Unacceptable Supplemental Yes Draft report for this study is expected in December 2015. 493730

- 02

835.4400 Anaerobic aquatic metabolism 429492

- 01 Supplemental Supplemental Yes Draft report for this study is expected in December 2015. 493730

- 02

835.1230 835.1240 Adsorption/ desorption and leaching 409454

- 03 Unacceptable Yes Soils were autoclaved in study. EFED requested a new study as part of the RED and a protocol for a leaching study (OCSPP 835.1240) was submitted and reviewed in 2011. Draft report for this study is expected in December 2015. Given acrolein’s rapid degradation in aquatic environments, the soil leaching study appears more appropriate than a batch equilibrium study.

835.6100 Terrestrial field dissipation -- -- No

835.6200 Aquatic field dissipation 415132

- 04/ 431769

- 01

418130

- 01/ 429491

- 01 Unacceptable

Unacceptable No MRID 431769

- 01 is a rebuttal of DER for MRID 415132

- 04. MRID 429491

- 01 is a rebuttal of DER for MRID 418130

- 01. Both studies had poor method recoveries.

850.6100 ECM

- Soil

-- -- No As irrigation water treated with acrolein is applied to a field and held for a period of 6 days prior to release, there is no anticipated need for a soil ECM.

850.6200 ECM

– Water 415132

- 04 Acceptable No Limit of quantitation is 10 μg/L.

3 ILV=independent laboratory validation

4 ECM=environmental chemistry method



### b. Effects

Table 1 0 and 1 1 identify ecological effect studies by MRID that offer data for each guideline requirement, as well as study classifications and whether or not further data are needed in order to support risk assessment. T he database for the acrolein TGAI is in complete

.

### Page 18 of 43 o The 40 CFR Part 158 (40 CFR 201 5 ) identifies data requirements for conventional pesticides, including those pesticides applied directly to water and/or those known to be phytotoxicants such as acrolein . Of the studies required to support the aquatic use of a crolein , the following studies are not available in the existing database and are therefore necessary for conducting an ecological risk assessment.

• Avian dietary toxicity test ( OCSPP 850.2200 19 

### ). Birds ( e.g ., water fowl) may forage plants in treated water and a broader range of birds may forage in agricultural fields/rangeland where acrolein

- treated waters may be applied with the intent of dissipating the compound ; therefore, there is a potential route of exposure. Currently, no subacute diet ary toxicity data are available for birds.

Tier II terrestrial plant vegetative vigor (OCSPP Guideline 850.4150) and seedl ing emergence (OCSPP 850.4250) have been submitted; however, the maximum rate tested in the seedling emergence study (0.088 lbs a

. i

. / A) and in the vegetative vigor study (0.086 lbs a

. i

. /A) is less than the maximum estimated rate (0.54 lbs a

. i

. /A) applied to agricultural fields in order to dissipate the compound.

Pollinator toxicity data consisting of an acute contact test with adult h oney bees (850.3020; OECD 214), acute oral test with adult honey bees (OECD 213), acute honey bee larvae test (OECD 237), 10

- day adult honey bee test (draft OECD guideline) and the 21

- day larval honey bee toxicity test (draft OECD guidance) are needed sinc e the current label allows for application to rangeland or to crops that may be in bloom, in which case bees may be exposed. Pending the outcome of the lower

- tier laboratory

- based acute and chronic toxicity studies of individual adult and larval honey bee s, higher

- tier studies, i.e ., semi

- field (OECD 75; 850.3030) and full

- field (850.3040) may be required. Appendix C provides rationales for each of the pollinator

- related data.

Table 10

. Submitted Aquatic Ecological Effects Data and Study Classifications for Acrolein.

OCSPP Guideline Data Requirement Study Type Submitted Studies (MRID) Study Classification Are data needed to conduct risk assessment Justification and Assumptions EPA will Make in Absence of Data

-

Some Example texts are include

850.1010 Freshwater invertebrate toxicity Acute Waterflea ( Daphnia mag na) 415132

- 02 Supplemental

No Acute toxicity test with D. magna resulted in a nondefinitive LC 50 <31 μg ai/L Waterflea ( Daphnia magna ) Acc. No. 05008271 Supplemental

850.1025 850.1035 850.1045 850.1055 Saltwater invertebrate toxicity Acute Eastern oyster Crassostrea virginica 402284

- 01 Acceptable

No

-- Brown Shrimp
Pe naeus aztecus 402284

- 01 Acceptable

19 USEPA. 2012. Ecological Effects Test Guidelines. OCSPP 850.2200: A vian Dietary Toxicity Test. Office of Chemical Safety and Pollution Prevention (7101) EPA 712

- C

- 024. January 2012. http://www.regulations.gov/#!documentDetail;D=EPA

- HQ

- OPPT

- 2009

- 0154

- 0011

### Page 19 of 43 OCSPP Guideline Data Requirement Study Type Submitted Studies (MRID) Study Classification Are data needed to conduct risk assessment Justification and Assumptions EPA will Make in Absence of Data

-

Some Example texts are include

Eastern oyster Crassostrea virginica 431643

- 02 Supplemental

Mysid shrimp Americamysis bahia 431643

- 01 Supplemental

850.1075 Freshwater fish Acute African clawed frog ( Xenopus laevis ) Holcombe et al. 1987 Supplemental

No Although freshwater fish acute toxicity tests are classified as supplemental, there is a sufficient concordance of information

to characterize hazard. Fathead minnow

( Pimephales promelas ) Holcombe et al. 1987 Supplemental

Bluegill sunfish ( Lepomis macrochirus )

415132

- 01 Supplemental

Rainbow trout ( Oncorhynchus mykiss ) 415132

- 03 Supplemental

Coho salmon ( Oncorhynchus kisutch ) 452051

- 07 Supplemental

850.1075 Saltwater fish Acute Longnose killifish Fundulus similis 402284

- 01 Acceptable

No

-- Sheepshead minnow Cyprinodon variegatus 432252

- 02 Supplemental

850.1300 Freshwater invertebrates life cycle Chronic Water Flea Daphnia m a gn a 0 5008271 Supplemental No The high acute toxicity of acrolein is expected to result in near complete mortality of aquatic organisms; the compound is expected to rapidly dissipate following treatment. Therefore, the

likelihood of chronic exposure is considered low.

850.1350 Saltwater invertebrates life cycle Chronic No data No

### Page 20 of 43 OCSPP Guideline Data Requirement Study Type Submitted Studies (MRID) Study Classification Are data needed to conduct risk assessment Justification and Assumptions EPA will Make in Absence of Data

-

Some Example texts are include

850.1400 Freshwater fish early

- life stage Chronic F athead minnow Pimephales promelas 0 5008271 Supplemental No The high acute toxicity of acrolein is expected to result in near complete mortality of aquatic organisms; the compound is expected to rapidly dissipate following treatment. Therefore, the

likelihood of chronic exposure is considered low.

850.1400 Saltwater fish early

- life stage Chronic No data No Likelihood of chronic exposure for estuarine/marine organisms considered low.

850.1500 Freshwater f ish full life cycle Chronic F athead minnow Pimephales promelas Sabourin 1986* Supplemental No Two different studies contained in the report by Sabourin

, i.e., 96

- hr LC 50 = 29.7 μg/L and 32

- day LC 50 =17.4 μg/L. Raw data were not available to substantiate toxicity estimates

. The high acute toxicity of acrolein is expected to result in near complete mortality of aquatic organisms; the compound is expected to rapidly dissipate following treatment. The refore, the likelihood of chronic exposure is considered low

850.1735 850.1740 10

- day Sediment Toxicity Test Subacute No data Acrolein is not expected to partition appreciably to sediment.

850.4400 Aquatic plant Toxicity Test using Lemna minor

. NA Duckweed Lemna gibba

426209

- 04 Supplemental No Although the study is classified as supplemental due to rapid dissipation of

test material, the DER indicates that the study does

not have to be repeated.

850. 540 0 Algal toxicity NA Green A lgae
Pseudokirchneriella subcapitata 426209

- 05 Acceptable

No According to DER for S. costatum, the study was upgraded to acceptable on 9/6/94 NA Freshwater D iatom Navicula pelliculosa 42609

- 02 Acceptable

NA Marine D iatom
Skeletonema costatum

426209

- 03 Supplemental

850.4550 Cyanobacteria NA Blue

- green A lgae Anabaena flos

- aquae 426209

- 01 Acceptable No

### Page 21 of 43 Table 1 1 . Submitted Terrestrial Ecological Effects Data for Acrolein

.

OCSPP Guideline Data Requirement Study Type Submitted Studies (MRID) Study Classifications Are data needed for risk assessment Current Additional Data Need

850.2100 Avian oral toxicity Acute Mallard 470214075 Acceptable

No Bobwhite quail study (LD 50 =19 mg/kg) is classified as supplemental due to absence of information on sublethal effects and the nature of controls used in the study. Mallard duck LD 50 of 9 mg/kg is considered protective for bobwhite. Bobwhite Accession No.

92001

- 003 Supplemental

Mallard

Anas platyrhynchus

421833

- 01 Acceptable

Passerine Acute No data No

850.2200 Avian dietary toxicity Subacute Mallard Anas platyrhnchus No data

Yes EPA waived the subacute dietary toxicity data requirement ; Document No.

2000782; dated 2/25/91

. However, exposure of birds

through diet treated with acrolein is a potential route of
exposure. Bobwhite Colinus virginianus No data

850.2300 Avian reproduction Chronic Mallard Anas platyrhnchus No data

No EPA waived the avian reproduction data requirement Bobwhite Colinus virginianus No data

Non

guideline Avian inhalation Acute No

850.3020 Honey bee acute contact toxicity Acute No data Yes Honey bee ( Apis mellifera ) acute contact toxicity data initially waived by EPA (Akerman memo dated 5/30/89) for Magnacide ® H use in irrigation canals (Document No. 2000784). In 2014, EPA issued honey bee risk assessment guidance indication both laboratory

based studies of individual bees as well as field

- based studies of bee colonies.

Special Study Honey bee acute oral toxicity Acute No data Yes In 2014, EPA issued honey bee risk assessment guidance indication both laboratory

based studies of individual bees as well as field

- based studies of bee colonies.

### Page 22 of 43 OCSPP Guideline Data Requirement Study Type Submitted Studies (MRID) Study Classifications Are data needed for risk assessment Current Additional Data Need

Special Study Honey bee larval toxicity test (OECD 237) Acute No data Yes

Special Study Honey bee adult 10

- day toxicity
test Chronic No Data Yes

Special Staudy Honey bee 21

- day larval toxicity test Chronic No Data Yes

850.3030 Honey bee residue on foliage NA No data Yes 1 Pending outcome of Tier 1 tests, studies held in reserve

.

850.3040 Field testing for pollinators Chronic No data Yes 1 Pending outcome of Tier 2 (semi

- field studies) , full

- field studies held in reserve.

850.4100 Seedling Emergence and Seedling Growth -- 486438

- 01 Supplemental * Yes Although EPA provided a review of the proposed protocol (DP Barcode D334821); the actual
treatment rates were not indicated in the protocol. Seedling emergence study evaluated maximum rate of 0.088 lbs ai/A and did not demonstrate any statistically signifi cant effect that was considered treatment related. The treatment rate evaluated is less than the maximum rate estimated for acrolein, i.e
., 0.54 lbs ai/A.

850.4250 Vegetative Vigor -- 486438

- 02 Supplemental * Yes Although EPA provided a review of the proposed protocol (DP Barcode D334821); the actual
treatment rates were not indicated in the protocol. Vegetative vigor study evaluated maximum rate of 0.086 lbs ai/A and did not demonstrate any statistically significa nt effect that was considered treatment related. The treatment rate evaluated is less than the maximum rate estimated for acrolein, i.e
., 0.54 lbs ai/A.

* Review of study has not been finalized.

### Page 23 of 43 12. References

Baker Petrolite Corporation.2006. Magnacide H herbicide Application by State. Submitted by Baker Petrolite Corporation. (MRID 46976913)

Baker Performance Chemicals. 1986 Washington Magnacide H Monitoring Report . Submitted by Baker Petrolite, Bakersfield , CA. (MRID 47008404)

Bonnivier, Bonnie, and Joseph Penkala. 2000. Magnacide H Herbicide Irrigation Dissipation in Kern County Water Storage Districts. Study conducted and submitted by Baker Petrolite, Bakersfield, CA. (MRID 47008403)

David, R. 1989. Ac ute Oral Toxicity Study of Acrolein, Inhibited in Rats: Final Report: Study G

- 7230.220. Unpublished study pre

- pared by Microbiological Associates, Inc. 87 p. (MRID 41257001)

Etzkorn, W. G. 2009. Acrolein and Derivatives. Kirk

- Othmer Encyclopedia of Chem ical Technology. 1

– 29.

Ghilarducci, D. P. and Tjeerdema, R. S. 1995. Fate and Effects of Acrolein. Reviews of Environmental Contamination and Toxicology 144:95

- 146.

Hoberman, A. 1991. Reproductive Effects of Acrolein Administered Orally via Gavage to Crl :CD (SD)BR Rats for Two Generations, with one Litter per Generation: Lab Project Number: 603/003: RD/ 0155/191 . Unpublished study prepared by Argus Research Laboratories, Inc. 1298 p. (MRID 41869101)

Holcombe, G. W., G. L Phipps, A. H. Sulaiman, and A.D. Hoffman. 1987. Simultaneous multiple species testing: Acute toxicity of 13 chemicals to 12 diverse freshwater amphibian, fish, and invertebrate families. Archives of Environmental Contamination and Tox icology 16 :697

- 710.

Hudson, R. H., R. K. Tucker, and M. A. Haegele. 1984. Handbook of Toxicity of Pesticides to Wildlif e

. Second Edition. U.S. Fish and Wildlife Service. Patuxent Wildlife Research Center. M RID 470214075.

Irwin, Katherine. 1988. Henry’s Law Constant for Acrolein (Magnacide H Herbicide and Magnacide B Microbiocide) . Performed by SRI International, 333 Ravenswood Avenue, Menlo Park, CA. Submitted by Baker Performance Chemicals, 3920 Essex Lane Houston, TX. SRI Project PYU 3562. (MRID 470084 01)

Matherly, R. Hackerott, J. Nguyen, N. 1987 Octanol/Water Partition Coefficient of Acrolein: Study No. RD0008.287. Unpublished study prepared by Baker Performance Chemicals. 24 p. (MRID 40840604)

Penkala, Joe. 2005. Acrolein Residual Analysis During Magnacide H Herbicide Application in Support of Air Quality Monitoring in Kern Delta Irrigation District, Bakersfield, CA. Submitted by Baker Petrolite Corporation, November 8, 2006. (MRID 47008407)

Preus, Martin W., and Charles L. Kissel. 1982. Control ling Plant Growth in Irrigation Systems: 1982 Nebraska Summer Research with Magnacide H. 1982 Nebraska Irrigation Expo & Water Conference. Performed by Magna Corporation, Santa Fe Springs, NM, and submitted by Baker Petrolite, Bakersfield CA. (MRID 469769 05)

### Page 24 of 43 Robillard, Kenneth A. Water Solubility of Acrolein. Performed by Health and Environmental Laboratories, Eastman Kodak Co. Rochester, NY. Study No. EN 040

- UKA001

- 1. Submitted by Baker Performance Chemicals.. Houston, TX. (MRID 40840602).

Salma, Tauseef. 2001. Henry’s Law Constant for Acrolein. Baker Petrolite Internal Memorandum to Miles Rhea, dated January 4, 2001.

Smith, A. M. 1993. ( 14 

### C

- Acrolein)

– Determination of the anaerobic aquatic metabolism. Unpublished study performed by Springborn La boratories, Inc., Wareham, MA; sponsored and submitted by Baker Performance Chemicals, Inc., Houston, TX. SLI Report # 91

- 3

- 3680, SLI Study # 12167

- 1089

- 6101

- 755. The experiment was initiated on November 9 and terminated on May 21, 1993 (p. 11). Final r eport issued September 22, 1993. (MRID 42949201)

Smith, A. 1993. (14C

- Acrolein)

-- Determination of the Aerobic Aquatic Metabolism Final Report: Lab Project Number: 91

- 3

- 3747: 12167

- 0789

- 6100

- 750. Unpublished study prepared by Springborn Laboratories, Inc. 125 p. (MRID 43227101)

Smith, Curtis W. 1962. Acrolein. John Wiley and Sons, London.

USEPA 2014. Conceptual Models for Environmental Exposure Pathways of Antimicrobial Pesticides. Office of Pesticide Programs, Antimicrobial Division, Risk Assessment and Science Support Branch. August 4, 2014. EPA

- HQ

- OPP

- 2014

- 0638. http://www.regulation.gov/#!documentDetail;D=EPA

HQ

- OPP

- 2014

- 0638

- 0002.

### Page 25 of 43 Appendix A. Bibliography of Submitted Studies

Environmental Fate

63

- 8 Solubility

MRID: 40840602 Robillard, K. (1988) Water Solubili ty of Acrolein: Laboratory Pro ject ID: HAEL No. 88

- 0300: Stu dy No. EN

- 040

- UKA001

- 1. Unpub lished compilation prepared by Health and Environment Laborato ries. 34 p.

63

- 9 Vapor Pressure

MRID: 40840603 Robillard, K. (1988) Vapor Pressure of Acrolein: Laboratory Project ID: HAEL No.: 88

- 0300: Study No. EN

- 030

- UKA001

- 1. Unpublished compilation prepared by Health and Environment Laboratories. 31 p.

63

- 1 1 Oct/Water partitio n Coefficient

MRID: 40840604 Matherly, R.; Hackerott, J.; Nguyen , N. (1987) Octanol/Water Parti tion Coefficient of Acrolein: Study No. RD0008.287. Unpublished study prepared by Baker Performance Chemicals. 24 p.

161

- 1 Hydrolysis

MRID: 40945401 Haag, W.; Yao, D.; Pettit, T.; et al . (1988) Estimation of Hydroly sis Rate Constants for Acrolein (Magnacide H Herbicide, Magna cide B Microbiocide) in the Environment: SRI Project No. 3562

- 3. Unpublished study prepared by SRI International. 54 p.

835.22 10 Direct photolysis rate in water by sunlight

MRID: 49373001 Roberts, G. (2014) Acrolein: Direct Photolysis Rate in Water by Simulated Sunlight. Project Number: 12/0055/B, BR0915/B. Unpublished study prepared by AstraZeneca UK, Ltd. 21p.

835.4 300 Aerobic aquatic metabolism

MRID: 42837601 Smith A.M. 1993. (14C

- Acrolein)

– Determination of the aerobic aquatic metabolism. Unpublished study performed by Springborn Laboratories, Inc., Wareham, MA; sponsored and submitted by Baker Performance Chemicals, Inc., Houston, TX. SLI Report: #91

- 3

- 3747; SLI Study #12167

- 0789

- 6100

- 750. Experiment initiated December 4, 1992, and completed February 1, 1993 (p. 11). Final report issued June 3, 1993.

MRID: 49373002 Daniel, M. (2014) (Carbon 14) Acrolein : Aerobic and Anaerobic Aquatic Metabolism, Preliminary

### Page 26 of 43 Study. Project Number: 120055I, BR0904/B. Unpublished study prepared by AstraZeneca UK, Ltd. 95p.

835.4400 Anaerobic aquatic metabolism

MRID: 42949201 Smith A.M. 1993. (14C

- Acrolein)

– Dete rmination of the anaerobic aquatic metabolism. Unpublished study performed by Springborn Laboratories, Inc., Wareham, MA; sponsored and submitted by Baker Performance Chemicals, Inc., Houston, TX. SLI Report # 91

- 3

- 3680, SLI Study # 12167

- 1089

- 6101

- 755. Th e experiment was initiated on November 9 and terminated on May 21, 1993 (p. 11). Final report issued September 22, 1993

MRID: 49373002 Daniel, M. (2014) (Carbon 14) Acrolein: Aerobic and Anaerobic Aquatic Metabolism, Preliminary Study. Project Number: 120055I, BR0904/B. Unpublished study prepared by AstraZeneca UK, Ltd. 95p.

Other

MRID: 46976905 Citation: Preus, M.; Kissel, C. (1982) Magnicide H Monitoring Program For the State of Nebraska. Project Number: RDSFS0018/188. Unpublished study prepared by Magna Corporation. 59 p.

MRID: 47008404 Citation: Rice, C. (2006) 1986 Washington Magnicide H Monitoring Report: Data Used to Support Special Local Needs SLN Registration Requested by the Washington State Water Resources Association: Acrole in. Unpublished study prepared by Baker Petrolite Corporation. 54 p.

Ecological Effects



## 71

- 1 Avian Single Dose Oral Toxicity

MRID Citation Reference

117668 2059323 Tucker, R.; Hudson, R. (1970) Acr olein: Acute Oral LD50 for Mallard Drakes . (Unpublished study received Mar 20, 1975 under 10707

- 9; prepared by U.S. Fish and Wildlife Service, Denver Wildlife Research Center, Unit of Physiological and Pharmacological Studies, submitted by Magna Corp., Sante Fe Springs, CA; CDL:165015

- A)

117672 2000882 Kresse, H. (1975) Laboratory Test Report: (Acrolein LD50 Bobwhite Quail): Laboratory Report No. K

- 1524. (Unpublished study received Sep 24, 1975 under 10707

- 9; prepared by MBA Laboratories, Inc., submitted by Magna Corp., Santa Fe Springs, C A; CDL: 223298

- A)

42183301 2000858 Pedersen, C.; Helsten, B. (1991) Acrolein: 21

- Day Acute Oral LD50 Study in Mallard Ducks: Lab Project Number: 118

- 001

- 04. Unpublished study prepared by Bio

- Life Associates, Ltd. 54 p.

### Page 27 of 43 92001003 2000882 Conn , R. (1990) Baker Performance Chemicals Inc. Phase 3 Summary of MRID 00117672. Determination of LD50 Acrolein

- Bobwhite Quail: Project K

- 1524. Prepared by MBA Laboratories, Inc. 10 p.

117675 Open lit

- not a mortality study Denine, E.; Robbins, S.; Kensl er, C. (1971) The effects of acrolein inhalation on the tracheal mucosa of the chicken. Taken from: Tox. & App. Pharm. 19(2):416. (Abstract 144; also In unpublished submission received Jun 17, 1976 under 201

- 118; submitted by Shell Chemical Co., Washington , DC; CDL:224738

- B) ton, DC; CDL:224738

- B)

0160000 2049115 or 2059323 Hudson and Tucker



## 71

- 5 Simulated or Actual Field Testing

MRID Citation Reference

32957 DER not located Bishop, J.L.; Penner, J.; McClelland, L. (1971) Aqualin^(R)I Herbicide in Irrigation Canal vs. Ducks. (Unpublished study received Oct 29, 1971 under 201

- 118; prepared in cooperation with Magna Corp. and East Contra Costa County (California), Irrigation Dis trict, submitted by Shell Chemical Co., Washington, D.C.; CDL:000772

- D)

67121 DER not located Shell Chemical Company (1971) Toxicity of Aqualin to Ducks and Muskrats. (Compilation; unpublished study received Oct 29, 1971 under 201

- 118; CDL:227781

- B)



## 7 2

- 1 Acute Toxicity to Freshwater Fish

MRID Citation Reference

34210 or 69192 No DER located

cited in reviews

- 2000822 Bond, C.E.; Lewis, R.H.; Fryer, J.L. (1960) Toxicity of various herbicidal materials to fishes. Pages 96

- 101, In Transactions of the 1959 Seminar of Biological Problems in Water Pollution. By Robert A. Taft Engineering Center. Cincinnati, Ohio: U.S. Public Health Service. (Technical report W60

- 3; published study; CDL:230691

- H)

95728 Open lit

- No DER

– cited in review 2000849 Bond, C.E. (1959) Letter sent to E.F. Feichtmeir dated May 20, 1959 Toxicity of F

- 98 to rainbow trout and chinook salmon. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Oregon State College, Experiment Station, Dept of Fi sh and Game Management, submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- H)

95729 DER not located Loeb, H.A. (1959) Letter sent to C. George Green dated Apr 7, 1959 Toxicity of F

- 98 to fishes. (New York, Conservation Dept., Div. of Fish and Game, Bureau of Fish Laboratory; unpublished study; CDL:000755

- I)

117661 DER not located New York, Conservation Dept. (1959 ) Preliminary Test : Lab Report No. 34. (Unpublished study received Oct 31, 1966 under unknown admin. no.; prepared by Div. of Fish and Game, Bureau of Fish

### Page 28 of 43 Laboratory, submitted by Shell Chemical Co., Washington, DC; CDL:106770

- D)

117662 DER not located Shell Chemical Co. (1954) Toxicity of Acrolein: Various Fish. (Unpublished study received Oct 31, 1966 under unknown admin. no.; CD L:106770

- E)

129075 or 45205107 Check EFED library

- EPA publications Lorz, H.; Glenn, S.; Williams, R.; et al. (1979) Effects of Selected Herbicides on Smolting of Coho Salmon. By Oregon, Dept. of Fish and Wildlife, Research and Development Section and U.S. Forest Service, Pacific Northwest Forest and Range Experiment Station. Corvallis, OR: US EPA. ( EPA

- 600/3

- 79

- 071 ; Grant #R

- 804283; pages i,iv

- x,1,6

- 14,40

- 50,83

- 85,92 only; also In unpublished submission received Jun 24, 1983 under 464

- 502; submitted b y Dow Chemical U.S.A., Midland, MI; CDL:250605

- N)

41513201 2000871 Bowman, J. (1990) Acute Flow

- through Toxicity of Acrolein to Bluegill ( Lepomis macrochirus ): Lab Project Number: 37669. Unpublished study prepared by Analytical Bio

- chemistry Laboratories

, Inc. 35 p.

41513202 2000891 2000893 Bowman, J. (1990) Acute Flow

- through Toxicity of Acrolein to Rainbow Trout ( Oncorhynchus mykiss ): Lab Project Number: 37670. Un published study prepared by Analytical Bio

- chemistry Laboratories, Inc. 285 p.

41513203 2000872 Bowman, J. (1990) Acute Flow

- through Toxicity of Acrolein to Rainbow Trout ( Oncorhynchus mykiss ): Lab Project Number: 37670. Unpublished study prepared by Analytical Bio

- chemistry Laboratories, Inc. 285 p.

34217 DER not located

summary paper? Sh ell Chemical Company (1965?) Acute Toxicity of Aqualin^(R)I Her

bicide to Fish. (Unpublished study received Jan 5, 1968 under 201

- 118; CDL:000755

- R)

117653 DER not located

FWS report ? Dewitt, J. (1962) Field and Laboratory Investigations on Acrolein as a Fish Poison. Progress rept ., Jun 1

- Dec 31, 1962. (Unpublished study received on unknown date under unknown admin. no.; submitted by Shell Chemical Co., Washington, DC; CDL:106752

- A)

5 008271 2000892 2059325 Macek, K.J.; Lindberg, M.A.; Sauter, S.; Buxton, K.S.; Costa, P.A. (1976) Toxicity of Four Pesticides to Water Fleas and Fathead Minnows. Duluth, Minn.: U.S. Environmental Protection Agency, Environmental Research Laboratory. (EPA re port no. EPA

- 600/3

- 76

- 099; available from: NTIS, Springfield, VA; PB

- 262 912)

34209 DER not located

referenced in 2000849 and 2000880 Burdick, G.E.; Dean, H.J.; Harris, E.J. (1964) Toxicity of Aqualin to fingerling brown trout and bluegills. New York Fi sh and Game Journal 11(2):106

- 114. (Also In unpublished submission received Jan 5, 1968 under 201

- 118; submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- C)

34210 Referenced in 2000849 Bond, C.E.; Lewis, R.H.; Fryer, J.L. (1957) Toxicity of Va rious Herbicidal Materials to Fishes. Pages 96

- 101 ,In Effects of Pesticides on Aquatic Life. By N.P. (Also In unpublished submission received Jan 5, 1968 under 201

- 118; submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- D)

### Page 29 of 43 34212 No DER locate d Shell Chemical Company (1954) Herbicide Toxicity to Fish. (Un

published study received Jan 5, 1968 under 201

- 118; CDL: 000755

- J)

ECOTOX 12665 2059322 Holcombe, GW. ECOTOX Article review Acute toxicity of 13 chemicals to 12 FW species including fish, inverts, and amphibians

E014314 2059321 Sabourin, T.D. 96 Hour Acute and 32 Day Toxicity with Fathead Minnow at Battelle Institute

- Review of open literature



## 72

- 2 Acute Toxicity to Freshwater Invertebrates

MRID Citation Reference

117660 Summary report

- No DER located Washington, Dept. of Fisheries (1959) Screening of Organic Herbicide Acrolein. (Unpublished study received Oct 31, 1966 under unknown admin. no.; prepared by Shellfish Laboratory

-- Point Whitney, Shellfish Management Unit, sub mitted by Shell Chemical Co., Washington, DC; CDL:106770

- B)

41513202 2000891 2000893 Blakemore, G. (1990) Acute Flow

- through Toxicity of Acrolein to Daphnia magna: Lab Project Number: 37671. Unpublished study pre

pared by Analytical Bio

- chemistry Laboratories, Inc. 269 p.

41513203 2000872 Blakemore, G. (1990) Acute Flow

- through Toxicity of Acrolein to Daphnia magna : Lab Project Number: 37671. Unpublished study pre

pared by Analytical Bio

- chemistry Laboratories, Inc. 269 p.

5008271 2000892 2059 325 Macek, K.J.; Lindberg, M.A.; Sauter, S.; Buxton, K.S.; Costa, P.A. (1976) Toxicity of Four Pesticides to Water Fleas and Fathead Minnows. Duluth, Minn.: U.S. Environmental Protection Agency, Environmental Research Laboratory. (EPA report no. EPA

- 600/3

- 76

- 099; available from: NTIS, Springfield, VA; PB

- 262 912)



## 72

- 3 Acute Toxicity to Estuarine/Marine Organisms

MRID Citation Reference

43164301 2000894 Bettencourt, M. (1994) Acrolein

-- Acute Toxicity to Mysid Shrimp ( Americamysis bahia formerly Mysidopsis bahia ) Under Flow

- Through Conditions: Final Report: Lab Project Number: 94

- 1

- 5148: 12167.0292.6106.515. Unpublished study prepared by Springborn Labs, Inc. 88 p.

43164302 2000873 Bettencourt, M. (1994) Acrolein

-- Acute Toxicity to Eas tern Oyster ( Crassostrea virginica ) Under Flow

- Through Conditions: Final Report: Lab Project Number: 94

- 2

- 5151: 12167.0292.6107.504. Unpublished study prepared by Springborn Labs, Inc. 88 p.

43225202 2000883 Bettencourt, M. (1994) Acrolein

-- Acute Toxicity to Sheepshead Minnow ( Cyprinodon variegatus ) Under Flow

- Through Conditions: Final Report: Lab Project Number: 94

- 1

- 5150: 12167.0292.6105. 505. Unpublished study prepared by Springborn Labs., Inc. 91 p.

### Page 30 of 43 45205107 2080863 2060320 2065167 2065167 20 65168 Lorz, H.; Glenn, S.; Williams, R. et al. (1979) Effects of Selected Herbicides on Smolting of Coho Salmon: Lab Project Number: R

804283: EPA

- 600/3

- 79

- 071. Unpublished study prepared by Corvallis Environmental Research Laboratory. 103 p.

53234 Summary

No DER located Shell Chemical Company ( 19?? ) Relative Toxicity of Herbicides to Estuarine Organisms. (Unpublished study received Jan 14, 1959 under unknown admin. no.; CDL:106744

- B)

40228401 2049116 2059324 USEPA Gulfbreeze Laboratory Studies

- s ee Fed Lab Data folder in SAN 3 species tested

- see 2000822 summary of data under Butler 1965



## 72

- 4 Fish Early Life Stage/Aquatic Invertebrate Life Cycle Study

MRID Citation Reference

32930 Not specific to Acrolein

DER not located Swabey, Y.H.; Schenk, C.F. (1962) Studies Related to the Use of Algicides and Aquatic Herbicides in Ontario. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washing

t on, D.C.; CDL:000768

- A)

34208 DER not located DeWitt, J.W.; Gooch, V.; Woodward, R. (1962) Field and Laboratory Investigations on Acrolein as a Fish Poison. (Unpublished study including letter dated Feb 11, 1963 from J.W. DeWitt to Eric Heuermann, received Jan 5, 1968 under 201

- 118; prepared in coop

eration with Humboldt State College, submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- B)

34209 DER not located Burdick, G.E.; Dean, H.J.; Harris, E.J. (1964) Toxicity of Aqualin to fingerling brown trout and bluegills. New York Fish and Ga me Journal 11(2):106

- 114. (Also In unpublished submission received Jan 5, 1968 under 201

- 118; submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- C)

34210 69192 DER not located Bond, C.E.; Lewis, R.H.; Fryer, J.L. (1957) Toxicity of Various Herbicidal Mat erials to Fishes. Pages 96

- 101, In Effects of Pesticides

o n Aquatic Life. By N.P. (Also In unpublished submission received Jan 5, 1968 under 201

- 118; submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- D)

34212 DER not located She ll Chemical Company (1954) Herbicide Toxicity to Fish|. (Un

published study received Jan 5, 1968 under 201

- 118; CDL: 000755

- J)

34214 DER not located Swabey, Y.H.; Schenk, C.F. (1963) Report on Algicides and Aquatic Herbicides. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- N)

138964 Open lit DER not located Folmar, L. (1976) Overt avoidance reaction of rainbow trout fry to nine herbicid es. Bulletin of Environmental Contamination & Toxicology 15(5):509

- 514. (Also In unpublished submission received Feb 6, 1984

### Page 31 of 43 under 239

- 2424; submitted by Chevron Chemical Co., Richmond, CA; CDL:252355

- D)

138965 Open lit DER not located Folmar, L. (1978) Avoidance chamber responses of mayfly nymphs exposed to eight herbicides. Bulletin of Environmental Contam

- ination & Toxicology 17:312

- 318 . (Also In unpublished submission received Feb 6, 1984 under 239

- 2424; submitted by Chevron Chemical Co., Richmond, CA; CDL:252355

- E)

46269 DER not located Swabey, Y.H.; Schenk, C.F. (1963) Report on Algicides and Aquatic Herbicides. (Ontario, Water Resources Commission, Laboratory Division, Biology Branch, unpublished study; CDL:107773

- B)

E014314 2059321 Sabourin, T .D. 32 Day Toxicity with Fathead Minnow at Battelle Institute

- Review of open literature



## 72

- 7 Simulated or Actual Field Testing

MRID Citation Reference

32930 DER not located Swabey, Y.H.; Schenk, C.F. (1962) Studies Related to the Use of Algicides and Aquatic Herbicides in Ontario. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washing

ton, D.C.; CDL:000768

- A)

32941 DER not locate d Battelle Memorial Institute (1970) Degradation and Depletion of Herbicides in Drainage Waters and Accumulation of Residues in Crops Irrigated with Treated Water: Final Report

-- Acrolein. (Unpublished study received Aug 7, 1970 under 201

- 118; submit

- ted by Shell Chemical Co ., Washington, D.C.; CDL:000760

- A)

34211 DER not located Shell Chemical Company (1959) Efficacy of Herbicides on Aquatic Species|: Project No. PR 59

- 1. (Unpublished study including project nos. P.R. 52

- 2 and 59

- 3, received Jan 5, 1968 under 201

- 118; CDL :000755

- E)

34214 DER not located Swabey, Y.H.; Schenk, C.F. (1963) Report on Algicides and Aquatic Herbicides. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- N)

95726 DER not located Schoeneman, D. (1959) Letter sent to E.F. Feichtmeir dated Nov 16, 1959 Herbicidal efficacy of acrolein and its effects on animals. (Washington, Dept. of Fisheries; unpublished study; CDL: 000755

- F)

95727 DER not located Lindsay, C.E. (1959) Letter sent to E.F. Feichtmeir dated Nov 9, 1959 Toxicity of acrolein as an algacide. (Washington, Dept. of Fisheries, Shellfish Laboratory, Shellfish Management Unit; unpublished study; CDL:000755

- G)

### Page 32 of 43 

## 123

- 2 Aquatic plant growth

MRID Citation Reference

42620901 2000875 Hughes, J.; Alexander, M. (1992) The Toxicity of Acrolein to Anabaena flos

- aquae: Lab Project Number: B962

- 01

- 2. Unpublished study prepared by Malcolm Pirnie, Inc. 36 p.

42620902 2000884 Hughes, J.; Alexander, M. (1992) The Toxicity of Acrolein to Navicula pelliculosa : Lab Project Number: B962

- 01

- 3. Unpublished study prepared by Malcolm Pirnie, Inc. 36 p

42620903 2000874 Hughes, J.; Alexander, M. (1992) The Toxicity of Acrolein to Skeletonema costatum : Lab Project Number: B962

- 01

- 4. Unpublished study prepared by Malcolm Pirnie, Inc. 36 p.

42620904 2000885 Hughes, J.; Alexander, M. (1992) The Toxicity of Acrolein to Lemna gibba G3: Lab Project Number: B962

- 01

- 5. Unpublished study prepared by Malcolm Pirnie, Inc. 34 p.

42620905 2000895 Hughes, J.; Alexander, M. (1992) The Toxicity of Acrolein to Pseudokirchneriella subcapitata [formerly Selenastrum capricornutum ]: Lab Project Number: B962

- 01

- 1. Unpublished study prepared by Malcolm Pirnie, Inc. 36 p.

95727 letter Lindsay, C.E. (1959) Letter sent to E.F. Feichtmeir dated Nov 9, 1959 Toxicity of acrolein as an algacide. (Washington, Dept. of Fisheries, Shellfish Laboratory, Shellfish Management Unit; unpublished study; CDL:000755

- G)



## 850.4225 Seedling emergence, Tier II

MRID Citation Reference

48643801 DER not located Porch, J.; Krueger, H.; Martin, K. (2011) Magnacide H Herbicide (Acrolein): A Tier II Toxicity Test to Determine the Effects of the Test Substance on Seedling Emergence of Ten Species of Plants: Final Report. Project Number: 458/101. Unpublished study prepared by Wildlife International, Ltd. 108p.



## 850.4250 Vegetative vigor, Ti er II

MRID Citation Reference

48643802 DER not located Porch, J.; Krueger, H.; Martin, K. (2011) Magnacide H Herbicide (Acrolein): A Tier II Toxicity Test to Determine the Effects of the Test

### Page 33 of 43 Substance on Vegetative Vigor of Ten Species of Plants: Final Report. Project Number: 458/102. Unpublished study prepared by Wildlife International, Ltd. 138p 

### 850.7100 Data reporting for environmental chemistry methods

MRID Citation Reference

49373003 DER not located Robinson, J. (2014) Acrolein and Potential Transformation Products: Validation of Analytical Methods. Project Number: 11/0089/D, BR0749/B. Unpublished study prepared by AstraZeneca UK, Ltd. 52p



# Non

- Guideline Studies

MRID Citation Reference

44359001 2059326 Schwab, D. (1997) The Effects of Magnacide H Plus in Irrigation Water on Lettuce Growth and Yield: Lab Project Number: 43776: ABC 43776R: 43776R. Unpublished study prepared by ABC Labs., Inc. 103
p.

68234 DER not located Bruns, V.F.; Yeo, R.R.; Arle, H.F. (1964) Tolerance of Certain Crops to Several Aquatic Herbicides in Irrigation Water. By U.S. Agricultural Research Service , Crops Research Div. in cooperation with the Washington, Montana, and Arizona Agricultura l Experiment Stations. Washington, D.C.: U.S. Dept. of Agriculture. (Technical bulletin 1229; available from U.S. Government Printing Office; published study; CDL:231431

- T)

117665 DER not located

- field trials see 2000822

- referenced Ferguson, F.; Blondea u, R. (1962) Report on Aqualin Herbicide

- mol

luscicide Trials in Sudan and Tanganyika: MHO/PA/102.62. (Un

published study received Dec 6, 1965 under unknown admin. no.; prepared in cooperation with World Health Organization , CDC Puerto Rico Field Station , submitted by Shell Chemical Co., Washington, DC; CDL:121123

- A)

34214 or 46269 Non specific DER not located Swabey, Y.H.; Schenk, C.F. (1963) Report on Algicides and Aquatic Herbicides. (Unpublished study received Jan 5, 1968 under 201

- 118; prepared b y Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washington, D.C.; CDL:000755

- N)

32930 DER not located

– field observations Swabey, Y.H.; Schenk, C.F. (1962) Studies Related to the Use of Algicides and Aquatic Herbicides in Ontario . (Unpublished study received Jan 5, 1968 under 201

- 118; prepared by Ontario, Water Resources Commission, submitted by Shell Chemical Co., Washing

ton, D.C.; CDL:000768

- A)

### Page 34 of 43 

### Appendix B

. Ecological Model Results

A. Screening Imbi bi tion Model (SIP; version 1.0)

Table 1. Inputs Parameter Value Chemical name Acrolein Solubility (in water at 25 o C; mg/L) 273.6

Mammalian LD 50 (mg/kg-bw) 10.3 Mammalian test species laboratory rat Body weight (g) of "other" mammalian species Mammalian NOAEL (mg/kg-bw) 3 Mammalian test species Body weight (g) of "other" mammalian species

Avian LD 50 (mg/kg-bw) 9.1 Avian test species mallard duck Body weight (g) of "other" avian species Mineau scaling factor 1.15 Mallard NOAEC (mg/kg-diet) 0 Bobwhite quail NOAEC (mg/kg-diet) 0 NOAEC (mg/kg-diet) for other bird species 0 Body weight (g) of other avian species 0 NOAEC (mg/kg-diet) for 2nd other bird species 0 Body weight (g) of 2nd other avian species 0

Table 2. Mammalian Results Parameter Acute Chronic Upper bound exposure (mg/kg-bw) 47.0592 47.0592 Adjusted toxicity value (mg/kg-bw) 7.9224 0.0000 Ratio of exposure to toxicity 5.9401 0.0000

Conclusion* Exposure through drinking water alone is a potential

concern for mammals Due to insufficient data, risk cannot be precluded

Table 3. Avian Results Parameter Acute Chronic Upper bound exposure (mg/kg-bw) 221.6160 221.6160 Adjusted toxicity value (mg/kg-bw) 4.7250 0.0000 Ratio of exposure to acute toxicity 46.9033 0.0000

Conclusion* Exposure through drinking water alone is a potential concern for birds Due to insufficient data, risk cannot be precluded

*Conclusion is for drinking water exposure alone. This does not combine all routes of exposure. Therefore, when aggregated with other routes ( i.e ., diet, inhalation, dermal), pesticide exposure through drinking water may contribute to a total exposure that has potential for effects to non-target animals.

### Page 35 of 43 

# Welcome to the EFED Screening Tool for Inhalation Risk This tool is designed to provide the risk assessor with a rapid method for determining the potential significance of the inhalation exposure route to birds and mammals in a risk assessment.


# Input

Application and Chemical Information
Enter Chemical Name Acrolein Enter Chemical Use Aquatic Is the Application a Spray? (enter y or n) n If Spray What Type (enter ground or air) air Enter Chemical Molecular Weight (g/mole) 56.06 Enter Chemical Vapor Pressure (mmHg) 2.68E+02 Enter Application Rate (lb a.i./acre) 0.534

Toxicity Properties
**Bird** Enter Lowest Bird Oral LD 50 (mg/kg bw) 9.1 Enter Mineau Scaling Factor 1.15 Enter Tested Bird Weight (kg) 0.178 **Mammal** Enter Lowest Rat Oral LD 50 (mg/kg bw) 10.3 Enter Lowest Rat Inhalation LC 50 (mg/L) 17 Duration of Rat Inhalation Study (hrs) 4 Enter Rat Weight (kg) 0.35


# Output Results Avian (0.020 kg ) Maximum Vapor Concentration in Air at Saturation (mg/m 3 ) 8.09E+05 Maximum 1

- hour Vapor Inhalation Dose (mg/kg) 1.02E+05 Adjusted Inhalation LD 50 8.37E+01 Ratio of Vapor Dose to Adjusted Inhalation LD 50 1.21E+03 Proceed to Refinements Maximum Post

- treatment Spray Inhalation Dose (mg/kg) not applicable Ratio of Droplet Inhalation Dose to Adjusted Inhalation LD 50 not applicable not applicable



### Results Mammalian (0.015 kg ) Maximum Vapor Concentration in Air at Saturation (mg/m 3 ) 8.09E+05 Maximum 1

- hour Vapor Inhalation Dose (mg/kg) 1.28E+05

### Page 36 of 43 Adjusted Inhalation LD 50 1.01E+03 Ratio of Vapor Dose to Adjusted Inhalation LD 50 1.26E+02 Proceed to Refinements Maximum Post

- treatment Spray Inhalation Dose (mg/kg) not applicable Ratio of Droplet Inhalation Dose to Adjusted Inhalation LD 50 not applicable not applicable



### Summary of contact and exposure estimates used for foliar applications and soil treatments of pesticides for Tier 1 risk assessments for bees.

### Page 37 of 43 

### Appendix C

. Pollinator Data Requirements

Study Title: Honey bee Adult Acute Oral Toxicity Rationale for Requiring the Data Terrestrial invertebrates are likely to be impacted if exposed to pesticides in various use settings

. With eusocial bees, pesticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive

. Therefore, potential acute effects to adult honey bee s and other insect pollinators from oral exposure to some pesticides could exist

. Currently available toxicity studies do not address possible effects of oral exposure on adult terrestrial insect survival

. Because of the potential for pollen and nectar to be contaminated with pesticide residues, and subsequently brought back to the hi ve, it is important to determine the acute oral toxicity of this compound to adult honey bee s and other insect pollinators.

The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate test species

. The guidances discusses Tier 1 laboratory

based acute oral toxicity studies of individual adult bees as a critical component of the screening

level risk assessment process for examining potential adverse effects from specific routes of exposure. The guidance can be found at: http://www2.epa.gov/pollinator

- protection/pollinator

- risk

assessment

- guidance

. Additional guidance on the honey bee oral toxicity test design can be found in OECD Test Guid eline 213 ( http://www.oecd

ilibrary.org/docserver/download/9721301e.pdf?expires=1423074617&id=id&a ccname=guest&ch ecksum=2F0764FCB4DCF01D32382952A2E995C3 ) Practical Utility of the Data How will the data be used? The Tier 1 acute oral toxicity d ata on adult honey bees serve as a foundation for the screening

- level assessment of potential risk non

- targe t organisms such as federally listed threatened or endangered and non

- listed terrestrial invertebrate insects, including pollinators, from acute oral exposures to pesticides. The data will be used to reduce uncertainties associated with the risk assessment for terrestrial invertebrates and will improve EPA’s understanding of the potential direct and indirect effects on a broad range of taxa. This study will also provide information with which to compare whether oral toxicity estimates differ from contact to xicity estimates obtained from other Tier 1 studies. If acute oral effects data for adult honey bees are not available, risks to terrestrial insects from acute oral exposure will be assumed.

How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect listed threatened or endan gered species and/or modify their designated critical habitat. Without these data, EPA may need to presume risk

, which will limit the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in use restrictions.

### Page 38 of 43 Study Titl e: Honey bee Larvae Acute Oral Toxicity Rationale for Requiring the Data Terrestrial invertebrates are likely to be impacted if exposed to pesticides in various use settings

. With eusocial bees, pesticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive where developing larvae and pupae may be exposed

. Therefore, potential adverse effects to developing bees could result from exposure to pesticide residues

. Available toxicity studies do n ot address possible effects on brood (larvae and pupae) survival/development

. Because of the potential for pollen and nectar to be contaminated with pesticide residues, and subsequently brought back to the hive, it is important to determine the acute toxic ity of this compound to bee brood

.
The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate test species

. The guidances discusses Tier 1 laboratory

based acute toxicity studies of individual honey bee larvae as a critical component of the screening

level risk assessment process for examining potential risks from specific routes of exposure. The guidance be found at: http://www2.epa.gov/pollinator

- protection/pollinator

- risk

- assessment

guidance

. Additional guidance on larval honey bee toxicity test design can be found in OECD Test Guideline 237 ( http://www.oecd

ilibrary.org/docserver/download/9713171e.pdf?expires=1422485600&id=id&accname=guest&ch ecksum=D8E07C2B1DF77BF096C3B29F55BF86A7 )

. In some cases, information pertaining to acute toxicity to honey bee larvae may be obtained with the chronic honey bee larval test thereby negating the need for separate acute and chronic larval toxicity tests. Pr actical Utility of the Data How will the data be used? The Tier 1 acute toxicity d ata on honey bee larvae serve as a foundation for the screening

- level assessment of potential risk to non

- target organisms including federally listed threatened or endangered and non

- listed terrestrial invertebrates , including pollinators, and/or modify their designated critical habitat from acute exposures to pesticides. The data will be used to reduce uncertainties associated with th e risk assessment for terrestrial invertebrates and will improve EPA’s understanding of the potential effects on terrestrial species and whether there is a differential sensitivity of larval bees relative to adult bees. If acute effects data for larvae are not available, risks to terrestrial insects from acute exposure will be assumed

.
How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect listed threatened or endangered species and/or modify their designated critical habitat. Without these data, EPA may need to presume ris k which will limit the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in use restrictions.

### Page 39 of 43 Study Title: Honey Bee Adult Chronic Oral Toxicity Rationale for Requiring the Data Terrestrial invertebrates are likely to be impacted if exposed to pesticides in various use settings

. With eusocial bees, p esticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive

. Therefore, potential chronic effects to adult honey bees and other pollinators from oral exposure to some pesticides could exist

. Currently available toxicity studies do not address possible lethal and sublethal effects of chronic oral exposure on adult terrestrial invertebrates and will assist in determining whether the sensitivity of adult bees differs from that of earlier life stages

. Because of the potential for pollen and nectar to be contaminated with pesticide residues, and subsequently brought back to the hive, it is important to determin e the chronic oral toxicity of this compound to adult honey bee s and other pollinators.

The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate test species

. The guidances dis cusses Tier 1 laboratory

based chronic oral toxicity studies of individual adult honey bee s as a critical component of the screening

- level risk assessment process for examining potential risks from specific routes of
exposure

. The guidance can be found at : http://www2.epa.gov/pollinator

- protection/pollinator

risk

- assessment

- guidance

. Although study design elements for the chronic 10

- day oral toxicity test with hon ey bees are similar to the OECD TG 213 acute oral toxicity test ( http://www.oecd

ilibrary.org/doc server/download/9721301e.pdf?expires=1422484908&id=id&accname=guest&ch ecksum=C38495D2A570AC2216CFB1F223D24AA7 ), EPA requires that the proposed protocol for this study be submitted for review and approval by EPA prior to initiating the test

. Practical Utility of the Data How will the data be used? The Tier 1 chronic toxicity d ata on adult bees serve as a foundation for the screening

- level assessment of potential risk to non

- target organisms including federally listed threatened or endangered species an d non

- listed terrestrial invertebrates , including pollinators, from chronic oral exposures to pesticides. The data will be used to reduce uncertainties associated with the risk assessment for terrestrial invertebrates and will improve EPA’s understanding o f the potential direct and indirect lethal and sublethal effects on a broad range of terrestrial species, particularly insect pollinators and to determine whether adult toxicity differs substantially from other life stages evaluated in other Tier 1 tests. If chronic oral effects data for adults are not available, risks to terrestrial insects from chronic exposure will be assumed.

How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect listed threatened or endan gered species and/or their designated critical habitat. Without these data, EPA may need to presume risk which will limit the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in use restrictions.

### Page 40 of 43 Study Title: Honey B ee Larvae Chronic Oral Toxi city Rationale for Requiring the Data Terrestrial invertebrates are likely to be impacted if exposed to pesticides in various use settings

. For eusocial bees, pesticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive where larvae and pupae may be exposed

. Therefore, potential effects to developing bees could result from chronic exposure to pesticide residues

. Available toxicity studies do not address possible c hronic effects on brood (larvae and pupae) survival

. Because of the potential for pollen and nectar to be contaminated with pesticide residues, and subsequently brought back to the hive, it is important to determine chronic larval/pupal toxicity and whethe r adult emergence is adversely affected. This study will provide information on whether honey bee larvae differ in sensitivity from adult bees following chronic exposure.

The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate test species

. The guidances discusses Tier 1 laboratory

based chronic toxicity studies of individual honey bee larvae as a critical component of the screening

- level risk assessment process for examining potential risks from specific routes of exposure. The guidance can be found at: http://www2.epa.gov/pollinator

- protection/pollinator

- risk

assessment

- guidance

. Additional information on larval honey bee toxicity repeat exposure test design can be found in the OECD draft guidance ( http://www.oecd.org/env/ehs/testing/Draft_GD_honeybees_rep_exp_for_2nd_CR_25_November _2013.pdf )

. Although study design elements for the chronic 21

- day toxicity test with honey bee larvae hav e been drafted, EPA requires that the proposed protocol for this study be submitted for review and approval by EPA prior to initiating the test. Practical Utility of the Data How will the data be used? The Tier 1 chronic toxicity d ata on bee larvae serve as a foundation for the screening

- level assessment of potential risk to non

- target organisms including federally listed threatened or endangered and non

- listed terrestrial invertebrates, including insect pollinators, from chronic

ex posures to pesticides

. These data will be used to reduce uncertainties associated with the risk assessment for terrestrial invertebrates and will improve EPA’s understanding of the potential direct and indirect lethal and sublethal effects on a broad range of terrestrial species, particularly insect pollinators. These data will also assist in determining whether early life stages of the bee differ in their sensitivity to pesticides relative to adults

. If chronic effects data for larvae are not available, ri sks to terrestrial insects from chronic exposure will be assumed.

How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect listed threatened or endangered species and/or modify their designated critical habitat

. Without these data, EPA may need to presume risk which will lim it the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in use restrictions

.

### Page 41 of 43 Study Title: Semi

- field Testing for P ollinators (tunnel or colony feeding studies) Rationale for Requiring the Data Tier 2 studies are conditional on the outcome of the screening

- level assessment where acute and/or chronic risk levels of concern have been exceeded for terrestrial invertebrates

. Terrestrial invertebrates are likely to be impacted if exposed to pesticides in va rious use settings

. For eusocial bees, pesticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive and may adversely affect developing brood (egg, larvae, and pupae) and adult bees

. Screening

- le vel (Tier 1 ) studies of individual bees do not address possible effects and/or exposure to pesticide residues at the colony

- level

. Because of the potential for pollen and nectar to be contaminated with pesticide residues, and subsequently brough t back to t he hive, it is important to determine whether bee colonies may be negatively affected under relatively controlled exposure conditions of a semi

- field study. In addition to providing effects data, these studies can provide data on pesticide residues in poll en/nectar of treated plants.

The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate test species. This guidance describes the tiered testing process and can be found
at: http://www2.epa.gov/pollinator

- protection/pollinator

- risk

- assessment

- guidance , Additional information on honey bee colony studies under semi

- field conditions can be found in the OECD Guidance 75 ( http://www.oecd.org/officialdocuments/publicdisplaydocumentpdf/?cote=env/jm/mono% 282007%2922& do clanguage=en )

. Due to the complexities of this study, EPA requires that the proposed protocol for this study be submitted for review EPA prior to initiating the test. Practical Utility of the Data How will the data be used? Tier 2 colony

- level data will be used to assess potential risk to non

- target organisms including listed and

non

- listed terrestrial social invertebrate species and to determine whether effects observed in the screening

level (Tier 1) laboratory

- based studie s of individual bees are evident in colony

- level studies under semi

- field conditions. The Tier2 semi

- field test of whole colonies is a relatively controlled study, i.e ., bees are confined to a specific area, that is designed to represent potential field

- le vel exposure and account for hive dynamics, which are not achievable from other pollinator studies. This study will be used to determine whether adverse effects to insect pollinators at the whole colony level, may result for the use of pesticides and will help to refine risk estimates derived in the screening

- level risk assessment for beneficial terrestrial invertebrates. Measured residues in pollen/nectar can also be used to refine risk estimates derived from model

- based or default values in the screening

- level assessment.

How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect federally listed threatened or endangered species or their designated critical habitat. Without these data, EPA may need to presume risk which will limit the flexibility of pesticide products to compl y with FIFRA and the ESA, and could result in significant use restrictions.

### Page 42 of 43 Study Title: Semi

- field Testing for P ollinators (tunnel or colony feeding studies) Rationale for Requiring the Data For eusocial bees, pesticide residues may be transferred to pollen and/or nectar of treated plants and subsequently brought back to the hive and may adversely affect developing brood (egg, larvae, and pupae) and adult bees. Tier 2 feeding studies are condi tional on the outcome of the screening

- level assessment where acute and/or chronic risk levels of concern have been exceeded for terrestrial invertebrates based on Tier 1 studies of individual bees. Feeding studies utilize free foraging bee colonies that a re “dosed” with specific quantities of test material and represent a means of ensuring exposure to the test material through spiked pollen and/or sugar solutions fed to the colony while still allowing the bees to forage freely

. Since bee colonies are not c onfined to enclosures, colonies can be exposed for longer duration periods without subjecting the bees to stress that typically results from Tier 2 tunnel studies

. Available toxicity studies of individual bees (Tier 1) conducted to support screening

- level assessments do not address possible effects and/or exposure to pesticide residues at the colony

- level

. It is therefore important to determine whether bee colonies may be negatively affected where bees are free foraging and have the option to collect/consum e alternative forage items beyond the spiked food. Since multiple dose levels can be more readily tested, feeding studies can help to define dose

- response relationships at the whole colony level.

The Office of Pesticide Programs has made available a guid ance regarding ecological testing for bees using the honey bee as a surrogate

. This guidance describes the tiered testing process and can be found at http://www2 .epa.gov/pollinator

- protection/pollinator

- risk

- assessment

- guidance

. Additional information on honey bee colony feeding studies can be found in the EPPO Guidance 170 ( www.nationalbeeunit.com/downloadDocument.cfm?id=191 )

. Although study design elements for the feeding study are available through the EPPO Guidance 170, EPA requires that the proposed protocol for this study be submitted for review and approval by EPA prior to initiating the test. Practical Utility of the Data How will the data be used? Tier 2 colony feeding data will be used to assess potential risk to non

- target organisms including listed and

non

- listed terrestrial social invertebrate species. The colony feeding study is designed to represent potential field

- level exposure and account for hive dynamics using longer duration exposure periods than are possible in Tier 2 tunnel studies. This study will be used to determine whether potential adverse eff ects to insect pollinators at the whole colony level when bees are able to forage naturally beyond the spiked food. Results from the feeding study will help to refine the screening

- level risk assessment for beneficial terrestrial invertebrates that were ba sed on Tier 1 studies on individual bees. Since feeding studies can help to define a dose

- response relationship at the colony level, the studies can provide a means of determining exposure thresholds below which the likelihood of adverse effects on colonie s may be low.

How could the data impact the Agency’s future decision

- making? The Tier 2 colony

- level data will be used to refine screening

- level risk estimates derived using Tier 1 laboratory

- based data on individual bees. The Tier 2 data will help to in form the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect federally listed threatened or endangered species or their designated critical habitat. Without these data, EPA may need to presume risk which will limit the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in significant use restrictions.

### Page 43 of 43 Study Title: Field Testing for Pollinators Rationale for Requiring the Data Tier 3 studies are conditional on the outcome of the screening

- level assessment (Tier 1) where acute and/or chronic risk levels of concern have been exceeded for terrestrial invertebrates and where Tier 2 studies either under semi

- field tunnel conditions and/or feeding studies have indicated potential adverse effects at the colony level

. Available toxicity studies from lower

- tier studies do not address possible effects and/or exposure to pesticide residues at the colony

- level under actual pesticide use conditions and where specific uncertainties regarding the likelihood of exposure and/or effects remain

. Full

- field studies also provide an opportunity to measure residues in pollen and nectar as well as various matrices (beebread, honey, wax) within the colony to ob tain a more realistic understanding of exposure.

The Office of Pesticide Programs has made available a guidance regarding ecological testing for bees using the honey bee as a surrogate

. This guidance describes the tiered testing process and can be found a t http://www2.epa.gov/pollinator

- protection/pollinator

- risk

- assessment

- guidance

. Additional information on honey bee colony studies under full

- field conditions c an be found in the OCSPP 850.3040 ( http://www.regulations.gov/#!documentDetail;D=EPA

- HQ

- OPPT

- 2009

- 0154

- 0018 )

. Useful guidance is also available through OCSPP 850.2500 (Field Testing of Terrestrial Wildlife http://www.epa.gov/ocspp/pubs/frs/publications/Test_Guidelines/ser ies850.htm ) Although design element for the full

- field colony

- level study are available through the 850.3040 and 850.2500, EPA requires that the proposed protocol for this study be submitted for review and approval by EPA prior to initiating the test; th e protocol should attempt to address specific uncertainties identified in lower

- tier studies. Practical Utility of the Data How will the data be used? Tier 3 colony

- level data will be used to further characterize potential risk to non

- target organisms including listed and non

- listed terrestrial social invertebrate species and to refine screening

- level risk estimates that were based on individual bee resp onses. The semi

- field test is a controlled study that is designed to represent potential field

- level exposure under relatively controlled conditions and account for hive dynamics, which are not achievable from lower

- tier pollinator studies. This study will be used to determine whether adverse effects to insect pollinators at the whole colony level, may result for the use of pesticides and will help to refine the screening

- level risk estimates for beneficial terrestrial invertebrates. This study will also be used to determine whether more refined (Tier 3) studies are needed to characterize risk.

How could the data impact the Agency’s future decision

- making? The data will inform the determination required under FIFRA or the ESA as to whether continued registration of a pesticide is likely to result in unreasonable adverse effects to non

- target species or is likely to adversely affect federally listed threatene d or endangered species or their designated critical habitat. Without these data, EPA may need to presume risk which will limit the flexibility of pesticide products to comply with FIFRA and the ESA, and could result in significant use restrictions.