Page 2 of 12 into terrestrial and aquatic environments. DHMP is slightly toxic to avian species on an acute oral basis and practically nontoxic to avian species on subacute dietary basis ; practically non

- toxic to mammals on an acute oral basis; practically nontoxic to slightly toxic to freshwater fish; and slightly toxic to aquatic invertebrates

. For the ecological risk assessment, including an endangered species assessment for all uses, t he A gency requires needing the algal toxicity data

.

Introduction

1H

- Pyrazole

- 1

- methanol, 3,5

- dimethy (Busan 1104) is also known as

d i m ethyl1 h ydroxy m ethyl p yrazole (DMHMP). DMHMP technical (93%) is a white solid granule with no odor, is highly soluble in water ( 49.4 g/l) and has a vapor pressure of

2.55 x 10 - 3 mm Hg at 2 0 °C. The first product containing DMHMP as an active ingredient was registered in the United States in 19 96 for use as a material preserva tive

. Currently there is only one end

- use product registered with DMHMP as an active ingredient for the material preservative use s listed in Table 1. The product is registered

for use a s a preservative for emulsion paints, adhesives, latex emulsions, liquid polishes and waxes, detergents, paper making chemicals and coating

. A Reregistration Eligibility Decision (RED) has not been issued by EPA for DMHMP because the initial registration

date was after the November 1984

, the mandated cutoff for initiatio n of the RED process.

Table 1. Registere d Product of DMHMP

Registration

No. Registration

Name Company

Name Formulation Type % of Active Ingredient

1448

- 351 BUSAN 1104 Buckman

Laboratories Inc. Ready

- to

- Use

Solution 93

EPA Reg. No. 1448

- 351

BUSAN 1104 BUSAN is a registered trademark. Active Ingredient:

IH

- Pyrazole

- 1

- methanol, 3,5

- dimethyl...93%

Busan 1104 is a preservative that is effective for the protection of emulsion paints, adhesives, latex emulsions, and liquid polishes and waxes.

EMULSION PAINTS: For in

- can preservation of emulsion paints, including acrylic,

butadiene

- stryene and PVA paints, add 0.025 to 0.4% (250 to 4,000 ppm) Busan 1104 based on the total weight of the formulation. The preservative can be added to the paint

or any aqueous raw materials incorporated into the paint.

ADH ESIVES : To protect adhesives, including natural gums, natural latex, PVA emulsions, synthetic gums, starched based adhesives (including non

- converted tapioca, corn, and potato starches) and animal glues (including those derived from hide, bone,Page 3 of 12 fish, blood or gel atin) or other adhesives, add 0.05 to 0.4% Busan 1104 based on the total weight of the formulation.

LATEX EMULSIONS: For the preservation of styrene

- butadiene, PVA, acrylic and vinyl chloride, or other latex emulsions, add 0.02 to 0.3% Busan 1104 based on the total weight of the emulsion.

POLISHES AND WAXES: To preserve water

- based polishes and waxes in

- can during storage, add 0.02 to 0.3% Busan 1104 based on the total weight of the product.

PAPERMAKING CHEMICALS AND COATINGS : To control the bacterial

de gradation of paper coatings, size press solutions, wet

- end starch slurries, wet

- end cooked starch, and other formulations used in papermaking, add 0.05 to 0.4% (500 to 4,000 ppm) Busan 1104 based on the total weight of the formulation. For pigment slurries (including clay, titanium dioxide, and calcium carbonate based slurries) add 0.03 to 0.3% (300 to 3,000 ppm) Busan 1104 based on the total weight of the formulation.

DETERGENTS: To prevent bacterial degradation during storage and to increase shelf

life o f biodegradable surfactants, add 0.05 to 0.5% (500 to 5,000 ppm) Busan 1104 by weight of the formulation.

The Agency has conducted a review of the available product chemistry, environmental fate, and ecotoxicity data for DMHMP

. The findings are summarized

below.

A. Product Chemistry Summary of DMHMP ( 93% TGAI)

Common Name: 1H

- Pyrazole

- 1

- methanol, 3,5

- dimethyl

- l;

Chemical Name: 3,5

- Dimethyl

- 1

- (hydroxymethyl)pyrazole 3,5

- Dimethyl

- 1

- hydroxymethylpyrazole (DMHMP) 3,5

- Dimethylpyrazole

- 1

- methanol 3,5

- Dimethyl

- 1H

- pyrazole

- 1

- carbinol

Trade and Other Names: BL

- 1104 ; DMHMP

IUPAC Name: (3,5

- dimethyl

- 1H

- pyrazol

- 1

- yl)methanol

OPP Chemical Code: 129074 CAS Registry Number: 85264

- 33

- 1

Case: 5035 Chemical Family: Pyrazole

Alcohol

Molecular Formula: C 6 H 10 N 2 O Molecular weight: 126.1582 g/mole

Molecular Structure:Page 4 of 12 Color: White

Physical State: Solid, granular

Odor: None

Stability: Stable ( to heat)

Sensitive to sun light & metal ions

. This material is stable if stored under proper

conditions

. . Reactive with oxidizing agents.

Oxidation/Reduction: Not an oxidizer or reducing agent . Do not contain oxidizing or reducing agents

.

Flammability : Not applicable for products which do not con ta in combustible liquids

. Flash Point: 87.3°C ( > 212 °F ) Explodability: Contains no explosive ingredients

.

Storage Stability: Stable: 3 month sample shows no degradation Accelerated storage stability (thermal stability) shows no degradation

.

Miscibility: Not applicable for products not intended to be diluted with petroleum solvents

.

Corrosion Characteristics: Not corrosive to packaging material . No corrosion

of metals

.

Dielectric breakdown voltage: Not applicable for products not intended to be used

around electrical equipment

pH: Not applicable for solids

.

UV/Visible absorption: Not Reported

.

Viscosity: Not applicable for solid products

.

Melting point: 77 ° C (sublimes)Page 5 of 12 Boiling Point: Not applicable.

Density: 1.183 g/cc

Dissociation Constant: pK = 11.4

Log K o/w : 0.9294

Solubilit ies : 49 .4 g/l Fat Solubility: 14.3 g/kg (± 18% dependent on temp. & stirring)

.

Vapor Pressure: 3.4 x 10 - 3 hPa at 20 ° C

2.55 x 10 - 3 mm Hg (0.00255 mm Hg)

Henry's Law Constant: 3.586E

- 008 atm

- m3/mole ( Source: EPI Suite)

Enf orcement Analytical

Method: HPLC (uses UV detection s ystem)

Estimated K

oc : 22.34 L/kg ( Source: EPI Suite)

All product chemistry data requirements have been satisfied for the active ingredient s DMHMP

. (Source: MRID s 4183250 1 to

- 04 )

.

B. Environmental Fate Summary

No risk assessment was performed for DMHMP at the time of the registration

. The Agency has since reviewed two environmental fate studies for DMHMP , as summarized in Table 2. The Agency's conclusions for the degradation, studie s are as follows.

Degradation Studies (Abiotic)

a. Hydrolysis

Does not hydrolyze in aqueous buffered pH 5, 7, 9 solutions that were incubated

in dark ness at 25 ° C for 30 days. The study is acceptable (MRID No. 41831301).

b. Photodegradation in water

Does not photodegrade in aqueous buffered pH 5 solution but appeared to have photodegraded slightly in buffered pH 7 and 9 solutions during 30 days of 12 hour/day irradiation with a xenon light at 25 ° C. Slightly degrades in pH of 7 & 9 (MRID No s . 4183130 2 & 42 363901 ).Page 6 of 12 Table 2 . Environmental Fate Data Summary for DMHMP

OPP Guideline Fate Studies Half

- Life Degradates Study Status

161

- 1 Hydrolysis
(30 days at 25 ° C) pH 5 pH 7 pH 9 Stable

Stable

Stable None

None

None Acceptable

MRID 41831301

161

- 2 Aqueous Photolysis
(30 days at 25 ° C) pH 5 pH 7 pH 9 Stable Slightly degrades Slightly degrades None

None

None Acceptable

MRID s 4183130 2

42363901

The Agency did not conduct an environmental fate assessment for DMHMP

because of lack of data. However, the Agency needs to conduct an environmental fate assessment for material preservatives (including DMHMP ) that may potentially pass through waste water treatment plants (WWTPs) and may be discharged into terrestrial and aquatic environments. For this asse ssment the Agency anticipates needi ng those data outlined on page 9 of this document

.

Water Quality

DMHMP is not identified as a cause of impairment for any water bodies listed as impaired under section 303(d) of the Clean Water Act, based on information provided at the Agency’s National Pesticides Cause of Impairment of Waters website (searched April 7, 2011) 1

. In addition, no Total Maximum Daily Loads (TMDL) have been developed

for DMHMP, based on information provided at the Agency’s National Pesticide TMDL web site (searched April 7, 2011) 2
http://www.epa.gov/owow/tmdl/ . More information on impaired water bodies and

TMDLs can be found at

. The Agency invites submission of water qu ality data for this pesticid e. To the extent possible, data should conform to the quality standards in Appendix A of the OPP Standard Operating Procedure: Inclusion of Impaired Water Body and Other Water Quality Data in OPP’s Registration Review Risk Assessment and Management Proces s (see: http://www.epa.gov/oppfead1/cb/ppdc/2006/november06/session1

- sop.pdf ), in order to ensure they can be used quantitatively or qualitatively in pesticide risk assessments.

C. Ecological Effects Summary

No ecological risk assessment was performed for DMHMP at the time of the registration. Available e cotoxicity guideline studies and the r esults are summarized in

1

. http://iaspub.epa.gov/tmdl_waters10/attains_nation_cy.cause_detail_303d?p_cause_group_id=885

2
http://iaspub.e pa.gov/tmdl_waters10/attains_nation.tmdl_pollutant_detail?p_pollutant_group_id=885&p_p ollutant_group_name=PESTICIDESPage 7 of 12 Table 2 . The Agency's conclusions for the terrestrial and aquatic effects studies are as

follows.

a. Toxicity to Terrestrial Animals

Birds, Acute and Subacute

DMHMP is slightly toxic to avian species on an acute oral basis (LD 50 759 mg/kg ) and practically nontoxic to avian species on subacute dietary basis (LC 50 >5620 ppm)

.

Toxicity to Mammals

DMHMP is practically non

- toxic to mammals on an acute oral basis.

There is currently no 2

- ge neration rat reproduction study but in the human health scoping document it has been identified as a data gap.

b . Toxicity to Aquatic Animals

Freshwater Fish and Invertebrates

DMHMP is practically nontoxic to rainbow trout (LC 50 123 ppm), slightly

toxic to bluegill sunfish (LC 50 78 ppm ) and slightly toxic to aquatic

invertebrates (EC 50 31.7 ppm)

.

c . Toxicity to Aquatic Plants

Freshwater Algae

No algal toxicity data have been submitted. For the ecological risk assessment, including an endangered species assessment for all uses, t he Agency anticipates needing the algal toxicity data outlined on page 9 of

this document

.

Table 3 . Ecotoxicity Data Summary for DMHMP

MRID No GUIDE

LINE COMMON

NAME TAXONOMIC

NAME TEST

TYPE %

AI STUDY

TIME DOSE

TYPE TOXI

CITY TOX

LEVEL NOEL STUDY

STATUS TOX

CATEGORY

Avian Acute Oral Toxicity

41832201 850.2200 (71

- 1) Bobwhite quail Colinus virginianus O 99 14 day LD 50 759 mgk 292 Acceptable Slightly

toxic

Avian Subacute Dietary Toxicity

41832001 850.2200 (71

- 2a) Mallard

duck Anas platyrhynchos D 99 8 day LC 50 >5620 ppm 1000 Acceptable Practically

nontoxic

41832002 850.2200 (71

- 2b) Bobwhite quail Colinus virginianus D 99 8 day LC 50 >5620 ppm 3160 Acceptable Practically

nontoxicPage 8 of 12 MRID No GUIDE

LINE COMMON

NAME TAXONOMIC

NAME TEST

TYPE %

AI STUDY

TIME DOSE

TYPE TOXI

CITY TOX

LEVEL NOEL STUDY

STATUS TOX

CATEGORY

Freshwater Fish Acute Toxicity

41832302 850.1075 (72

- 1) Rainbow

trout Oncorhynchus mykiss S 99 96 hr LC 50 123 ppm 56.6 Acceptable Practically

nontoxic

41832301 850.1075 (72

- 1) Bluegill

sunfish Lepomis

macrochirus S 99 96 hr LC 50 78 ppm 34.5 Acceptable Slightly

toxic

Freshwater Invertebrate Acute Toxicity

41832303 850.1010 (72

- 2 ) Water

flea Daphnia

magna S 99 48 hr EC 50 31.7 ppm 24 Acceptable Slightly

toxic

Mammalian Acute Oral Toxicity

41832101 81

- 1 Rat

----- ----- --- ----- LD 50 26 00 m g/kg

bw ----- Acceptable Practically

non

- toxic

III

Test Type

— O: oral; D: dietary; S: static

. Tox Level

— mgk : milligrams per kilogram

- body weight; ppm : parts per million (equivalent to milligrams per kilogram

- diet (mg/kg

- diet) for dietary exposure and milligrams per liter (mg/L) fo r aq uatic exposures ) Categories of acute toxicity for aquatic organisms (U.S. EPA, 2004) based on E C 50 / LC 50 (mg/L): < 0

. 1 very highly toxic; 0.1

- 1 highly toxic;

> 1

- 10 moderately toxic; > 10

- 100 slightly toxic; > 100 practically nontoxic. Categories of acute toxicity to terrestrial animals, avian and mammalian (U.S. EPA, 2004). LC 50 (ppm): < 50 very highly toxic; 50

- 500 highly toxic; 501

– 1000 moderately toxic; 1001

- 5000 slightly toxic; >5000 practically non

- toxic. LD50 (mg/kg bw): < 10 very highly toxic;

1 0

- 50 highly toxic; 51

- 500 moderately toxic; 501

- 2000 slightly toxic; >2000 practically non

- toxic.

Adverse Ecological Incidents

There are no reported incidents in the Agency' s Ecological Incident I nfo rm ation System (EII S) regarding DMHMP

. The absence of documented incidents does not necessarily mean that such incidents did not occur.

Ec ological Effects Risk Assessment

An ecological risk assessment was not conducted on the DMHMP’s use patterns
described in this document. DMHMP uses that have potential for environmental exposure are material preservatives discharges. The Agency needs to conduct environmental fate and ecological risk assessments for material preservatives that potentially pass through waste water treatment plants (WWTPs) and ma y be discharged into terrestrial and aquatic environments. For this ecological risk assessment, including an endangered species assessment for all uses, t he Agency anticipates needing the algal toxicity data outlined on page 9 of this document

.

The Agenc y has not conducted a risk assessment for DMHMP that supports a complete endangered species effects determination. The ecological risk assessment planned during registration review will allow the Agency to determine whether 1H

Pyrazole

- 1

- methanol, 3,5

- dim ethyl

- ’s use has “no effect or “may affect” federally listed threatened or endangered species (listed species) or the ir designed critical habitats. When an assessment concludes that a pesticide’s use “may affect” a listed species or its designated critical habitat, the Agency will consult with the U.S. Fish and Wildlife Service and/or National Marine Fisheries Services (the Services), as appropriate.Page 9 of 12 Environmental Fate and Ecotoxicity Data Gaps and Anticipated Work

Environmental fate and ecological risk assessments have not been conducted for

DMHMP . The Agency needs to conduct environmental fate and ecological risk assessments for material preservatives that potentially pass through waste water treatment plants (WWT Ps) and may be discharged into terrestrial and aquatic environments. Therefore, the Agency anticipates needing the proposed environmental fate and ecotoxicity data for DMHMP and/or any of its major degradation products that are of potential concern for al l registered uses of DMHMP . The following environmental fate and ecotoxicity data are needed to conduct an environmental fate and ecological risk

assessment:

**•** The Agency anticipates needing the following data to conduct a complete

environmental fate asses sment for material preservative uses:

o (GLN 850.6800) Modified Activated Sludge Respiration Inhibition ;

o (GLN 835.3110) Ready biodegradability, (GLN 835.3220) Porous Pot Test, or (GLN 835.3280) Simulation Tests to Assess the Biodegradability

of Chemicals Di scharged to Wastewater 3

.

**•** The Agency anticipates needing the following algal toxicity data in order to conduct a complete ecological risk assessment, including an endangered species assessment:

o (GLN 850.5400) A lgal toxicity (Tier II) using freshwater gre en alga, Selenastrum capricornutum.

3 The results of the Activated Sludge Respiration Inhibition Test (ASRI) determine which of these biodegradation tests are required. If th e ASRI test EC 50 is less than or equal to 20 mg/L, then either the Biodegradation in Activated Sludge Study or the Porous Pot Test is required. If the ASRI test EC 50 is greater than 20 mg/L, then the applicant must choose either: (i) Ready Biodegradabilit y or (ii) Biodegradation in Activated Sludge or the Porous Pot Test. If the antimicrobial passes the ready biodegradability study, then no further testing is required. If, however, the antimicrobial fails the ready biodegradability study, then the Biodeg radation in Activated Sludge or the Porous Pot study is required.Page 10 of 12 

### Appendix A. Environmental Fate Guideline Study Justifications

Guideline Number: 850.6800; OECD 209 Study Title: Modified Activated Sludge, Respiration Inhibition Test for Sparingly Soluble Chemicals; Activated Sludge Respiration Inhibition Test
Rationale for Requiring the Data An activated sludge, respiration inhibition test (ASRI) is needed to identify whether this pesticide could harm activated sludge microorganisms found in biological wastewater treatment systems. The Agency

will use these data to determine the potential imp act of this chemical on waste water treatment plants (WWTPs) as a result of respiration inhibition of activated sludge microorganisms. This test is also necessary to enable EPA to establish correct concentrations for use in the biodegradability test, if th at test is determined to be adequate for assessing biodegradation potential. Furthermore, the results of the Activated Sludge Respiration Inhibition Test (ASRI) determine which biodegradation test is required. If

the ASRI test EC 50 is less than or equal t o 20 mg/L, then either the Biodegradation in Activated Sludge Study or the Porous Pot Test is required. If the ASRI test EC 50 is greater than 20 mg/L, then the applicant must choose either: (i) Ready Biodegradability or (ii) Biodegradation in Activated Sl udge or the Porous Pot Test. If the antimicrobial passes the ready biodegradability study, then no further testing is required. If, however, the antimicrobial fails the ready biodegradability study, then the Biodegradation in Activated Sludge or the Poro us Pot study is required.

Practical Utility of the Data

1. How will the data be used? The data will be used to assess potential adverse effects to activated sludge microorganisms. In addition,

the data will be used to determine whether or not label restrictions are needed. The study will identify the inhibitory effect of this chemical on the treatment plant’s microorganisms’ respiration at different concentrations of the test substance and will identify the EC 50 , the effective concentration of the t est substance at which the respiration rate is 50% of that shown by the control under conditions in this guideline. The data will also determine suitable non

- inhibitory concentrations to be used in biodegradability tests.

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

- making? If the data indicate a high degree of activated sludge respiration inhibition, a more rigorous test for biodegradation in wastewater treatment will be required than the ready biodegradability test. Also, if a high degree of respiration inhibition is demonstrated and biodegradation and/or sorption is indicated to be negligible, the Agency may require label restrictions or mitigation measures to insure that activated sludge microorganisms will not be adversely impacted.Page 11 of 12 Guideline Numbers: 835.3110, 835.3220, or 835.3280 Study Titles: Ready Biodegradability, Porous Pot Test, or Simulation Tests to Assess the Biodegradability of Chemicals Discharged to Wastewater (also referred to as Biodegradation in

Activated Sludge), respectively Rationale for Requiring the Data For antimicrobial chemicals that go down

- the

- drain and reach a WWTP, as part of its screening

- level environmental fate assessment, EPA will analyze the potential impact of the antimicrobial chemical on the microorganisms in the biological treatment process es of a WWTP. Biodegradation is an important environmental pathway in which the antimicrobial is broken down by bacteria. This study results suppl y information on the rate of biological breakdown and the completeness of the degradation to carbon dioxide

an d water. A ready biodegradability study would allow the Agency to determine whether or not the chemical achieves ‘‘pass levels’’ for ready biodegradability (e.g., 70% removal of dissolved organic carbon). The results of the Activated Sludge Respiration Inh ibition Test (ASRI) determine which of these three biodegradation tests are required. If the ASRI test EC 50 is less than or equal to 20 mg/L, then either the Biodegradation in Activated Sludge Study or the Porous Pot Test is required. If the ASRI test EC 50 is greater than 20 mg/L, then the applicant must choose either: (i) Ready Biodegradability or (ii) Biodegradation in Activated Sludge or the Porous Pot Test. If the antimicrobial passes the ready biodegradability study, then no further testing is requi red. If, however, the antimicrobial fails the ready biodegradability study, then the Biodegradation in Activated Sludge or the Porous Pot study is required. Practical Utility of the Data

1. How will the data be used?

The data from a biodegradation study will be used to determine the percent removal of the antimicrobial as a result of biodegradation of the antimicrobial by activated sludge microorganisms. Percent removal via biodegradation is a key input used to determine concentrations of the antim icrobial in surface water immediately downstream of wastewater treatment plants. The concentrations of antimicrobial pesticide immediately downstream of wastewater treatment plants are used to assess exposure and risk to non

- target endangered and non

- enda ngered species. Exposure data are integral parts of the risk equation for determining the impact of pesticides to beneficial non

- target organisms through direct exposure from their

food sources and habitat.

In addition, the data will be used to determine whether or not additional studies and/or label restrictions are needed. If the chemical does not achieve a ‘‘pass level’’ for ready biodegradability, then the Agency would determine that the chemical has the potential to pass through the WWTP and therefo re may be discharged in to the aquatic environment potentially resulting in exposure to non

- target species. This determination would trigger further data requirements to assess the chemical’s impact on the aquatic environment upon release.

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

- making? If the chemical is found to be readily biodegraded, then activated sludge microorganisms would be identified as highly biodegradable (90% removal via biodegradation). This result would be used in conju nction with wastewater treatment plant influent volume and measurement endpoints for aquatic organisms to determine concentrations of antimicrobial pesticide downstream of wastewater treatment plants. If high inhibition of activated sludge microorganisms (i.e., EC50 less than or equal to 20 mg/L) is determined in an activated sludge respiration inhibition test, then higher

- tiered wastewater treatment plant (WWTP) biodegradation studies and/or an activated sludge sorption isotherm study may be triggered. I f results of higher

- tier WWTP biodegradation tests indicate low or negligible removal by biodegradation, the risk assessments for this chemical would reflect the magnitude of potential risk derived from the chemical’s lack of biodegradability. The risk as sessment may result in the Agency requiring label restrictions that would be necessary for the products to meet the “no unreasonable adverse effects” requirements of FIFRA (e.g., changes to the directions for disposal).Page 12 of 12 In addition, EPA is required by sec tion 7(a)(2) of the ESA to ensure that any action it authorizes or takes “...is not likely to jeopardize the continued existence of any endangered or threatened species or result in

the destruction or adverse modification of critical habitat” and to use the best scientific data available” in carrying out this obligation. The data EPA intends to call in are necessary to inform the determination required by the ESA as to whether continued registration of a pesticide is not likely to jeopardize the species or i ts critical habitat. Absent this data EPA may not be able to conclude that this pesticide will not harm endangered species and may therefore need to consider other limitations on the use of the pesticide in order to fulfill the Agency’s statutory obligati ons under the ESA. The lack of these data will limit the flexibility that the Agency and registrants have in coming into compliance with the ESA and could result in use restrictions which are unnecessarily severe.



### Appendix B: Ecological Guideline Study Justifications

Guideline Number: 850.5400 Study Title: Algal toxicity (Tier II) using freshwater green alga

, Selenastrum capricornutum
Practical Utility of the Data 1) What is the value of the study? As part of an initial risk assessment, one indicator plant species is tested for phytotoxicity. This study would allow the Agency to categorize DMHMP as toxic or non

- toxic to plants. If toxic, additional higher tier plant tests would be needed. An endan gered species assessment for endangered or threatened plants is not possible without this study.

2) How would the data be used? This study would be used to evaluate the toxicity of DMHMP to non

- target plants in terrestrial and aquatic

ecosystems.

3) How could the d ata affect the risk assessment?

Adverse effects to non

- target plants in terrestrial and aquatic ecosystems may result in mitigation to protect species at risk. Mitigation might include reduced label dosages, neutralization of effluents prior to discharge into water, restrictions on use in sensitive ecosystems or where endangered species are present, or other mitigation measures.

4) What is triggering the need for this data? Increased concern from state regulators and the public to evaluate impa cts on WWTP operations, endangered species, and persistence in the environment, since initial registration, have triggered the need for this study. Green algae are critical to ecosystem health and productivity.