### UNITED STATES ENVIRONMENTAL PROTECTIONAGENCY WASHINGTON D.C., 20460

OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION 

### September 24, 2012


### MEMORANDUM
SUBJECT:

FROM:

THRU:

TO: Product Chemistry, Environmental Fate, and Ecological Effects Scoping Document in Support ofRegistration Review ofAmmonium Bromide

PC Code: 000352 DP Barcode: 401471 Decision No.: 464378 Registration Nos.: See Table 1 Petition No(s).: NA Regulatory Action: Ecological Environmental Scoping Document for Registration Review Risk Assessment Type: Single chemical Case No.: 5002 TXRNo.:NA CAS No.: 12124-97-9 MRID Nos.: See Tables 7, 8, & 9 and 40 CFR: None pages 4, 11, and 15 

### Srinivas Gowda, M.S.

### Microbiologist/**~c~ce** Coordinator

### Sa--l~"~~ William Erickson, Ph.D.,**Biologis~/i /~**  

### Najm Shamim, Ph.D., Chemist 

# 1\fJ

# /l[aA

....,.... . Risk Assessment and Science Support Branch (RASSB) Antimicrobials Division (751OP) Steven Weiss, Acting Branch Chief 

# ;iit'**~** DonnaRandall, M.S. Ecological Risk Assessment Team Leader Risk Assessment and Science Support Branch (RASSB) Aritimicrobials Division (751OP) Rebecca von dem Hagen, Chemical Review Manager Regulatory Management Branch II Antimicrobials Division (751OP)

Page 1 of 16Executive Summary Ammonium bromide is registered for use as an algicide, bactericide, microbicide and slimicide for treating industrial process and water systems such as recirculating cooling towers and pulp and papermills, and wastewater treatment systems. End use products ofammonium bromide are used in conjunction with an oxidant such as sodiumhypochlorite (12.5%) or chlorine gas (99.9%) under controlled conditions within an approved feeder/delivery system to produce monochloramine biocide 

### in situ. The monochloramine biocide is added to the water to be treated immediately as it is formed to control algal, bacterial and fungal slimes. Ammoniumbromidehas no pesticidal activity per se. Rather, it dissociates in water to ammonium anion (NH/) and bromide cation (Br-; bromine is in a -1 oxidation state here). However, ammoniumbromide converts to a hypobromite cation (BrO-; bromine is inthe+1 oxidation state) and monochloramine (NH2Cl) when mixed with sodiumhypochlorite or chlorine gas, which act as the disinfectants. Ammoniumbromide was initiallyregistered as a pesticide in the United States inJanuary 1999 for use as a bacteriocide and slimicide inrecirculating cooling water systems and pulp and paper mills. Currently it is used in five active products, two ofwhich are technical chemicals. All product chemistry data requirements have been satisfied for this active ingredient ammonium bromide. Conventional fate data for ammoniumbromide, monochloramine, and hypobromite is not required because these are inorganic compounds for which this type ofdata is not applicable. The Agency has evaluated the existing chemical information and properties on these compounds, their reaction products and ammoniumbromide use patterns and has determined that no additional data are required for reregistration review. The environmental fate ofthese compounds is complex but is known based on inorganic and oxidation/reduction chemistry. Hypobromite is a bleaching agent and germicide. Thehypobromite cation is not stable and converts into bromide ultimately; conditions in these systems are not considered favorable for the conversion to bromate. More recent data indicates that monochloramine is not stable in aquatic medium and it is biodegradable in water, and in sediments and possibly in soils. For the given ammonia bromide uses, resulting monochloramine residuals are not expected to persist long enough in industrial water systems to reach the aquatic environment. Technical-grade ammoniumbromide is practically nontoxic to birds. However, when ammonium bromide is combined with sodiumhypochlorite, the resultant monochloramine is highly to very highly acutely toxic to freshwater and estuarine/marine organisms. No additional ecological effects data are needed for these chemicals. Monochloramine is not expected to reach the aquatic environment. Therefore, an ecological risk assessment will not be conducted for the current uses ofammoniumbromide. The Agency anticipates the registered uses will have "no effect" on endangered or threatened terrestrial or aquatic species, ortheir designated critical habitats, as listed by the USFWS and the NOAA.

Page 

### 2 of 16

### Introduction Ammoniumbromide is an inorganic nitrogen and bromine compound registered for use as an algicide, bactericide, microbicide and slimicide for treating industrial process and water systems such as recirculating cooling towers and pulp and papermills, which includes their wastewater treatment systems. Ammonium bromide is used in conjunction with an oxidant such as sodium hypochlorite (12.5%) or chlorine gas (99.9%) to produce monochloramine biocide within an approved Fuzzicide®feeder/delivery system. Ammoniumbromide was initially registered as a pesticide in the United States in January 1999 for use as a bacteriocide and slimicide in industrial process waters ofrecirculating cooling towers and pulp and paper mills. Currently it is used in five active products, two ofwhich are technical products and three which are end-use products. Technical grade products are solid materials and have declared active ingredient content of99%. Two ofthe three end use products are solids with declared ammoniumbromide content of99%, the other end use product is a ready-to-use solution with a declared active ingredient content of35%. Summary information about these products is listed inTable 1. Ammonia bromide is currently registered for use as a bacteriocide and slimicide in industrial process waters ofrecirculating cooling towers and pulp and paper mills, which includes their sewage and wastewater treatment systems (Table 2). No ecological risk assessment was previously been performed for ammonium bromide. A Reregistration Eligibility Decision (RED) has not been issued by the Agency for ammonium bromidebecause the initial registration date was after the November 1984, the federally mandated cutofffor initiation ofthe RED process. 

### Table 1. Registered Products ofAmmonium Bromide Registration# Registration Name Company Name Formulation Type %ofActive Ingredient 8622-58 Fuzzicide-Comp ICL-IP America, Inc. Soluble Concentrate 99 8622-59 Ammonium Bromide-Comp ICL-IP America, Inc. Technical Chemical 99 8622-64 Fuzzicide Solution ICL-IP America, Inc. Ready-to-Use 35 Solution 8622-75 Ammonium Bromide-SP ICL-IP America, Inc. Technical Chemical 99 8622-76 Fuzzicide-SP (Ammonium ICL-IP America, Inc. Soluble 99 Bromide) Concentrate/Solid



### Page 3 of 16

### Table 2 - Ammonia Bromide Antimicrobial Use Summary Use Site (Treatment Site) Application Application Rate Notes Method Industrial Process Systems Recirculating cooling systems: Industrial cooling towers, evaporative condensers, heat exchange water towers, influent 0.3-5.0 ppm of systems such as flow through Metering residual Nonauthorized, filters, industrial water scrubbing (Enclosed feeder/ monochloramine nontrained personnel systems, brewery pasteurizers, delivery system) expressed as total cannot operate system sewage systems (septic tanks, leach chlorine in process fields, tank lines, sewers, lagoons, system' and sewage effluent water), industrial air-washing systems equipped with a mist eliminator PulQ and PaQer Mills (Pulp and paper mill fresh and sea water 0.3-10

.0 ppm of influent systems, and associated residual cooling water systems and Metering monochloramine Nonauthorized, wastewater treatment systems, pulp, (Enclosed feeder/ expressed as total nontrained personnel paper and paper board mill systems, delivery system) chlorine in process cannot operate system nonpotable water systems, starch system' slurries, and other process water that may contact food) 1While the amount ofammonia bromide end use product and sodium hypochlorite or chloride gas aqueous solution to add to the feeder box is listed onthe label, the amount actually applied per a given volume ofprocess water is not specifically designated-operator adds sufficient dosage to maintain a designated residual (unreacted) monochloramine in the process water. 

### A. Product Chemistry Summary ofAmmonium bromide (100% TGAI) Chemical identity and the physical and chemical properties ofthe ammoniabromide technical grade active ingredient (TGAI) are provided in Tables 3 and 4, respectively. The primary source ofinformation for this assessment was MRID Nos. 44711101 and 44683601. All product chemistry data requirements have been satisfied for the active ingredients sodium bromide. 

### Table 3. Chemical Identity Chemical Name Ammonium bromide Common Name Ammonium bromide Classification Inorganic PC Code 000352 CAS No. 12124-97-9 Molecular Formula NHJ3r
Page 4 of 16Molecular Weight 97.95 g/mole 

### H 

## (±) I 

# s.S Molecular Structure: I ,, 

## /**~** 

## .i";'H 

## H H

Table 4. Product Chemistry Data Summary ofAmmonium bromide (99% TGAI) OPPTS Physical and Chemical Value Guideline 

### No. Properties 830.1550 Product identity and Refer to Table 3. composition 830.1800 Enforcement analytical Potentiometric titration. method HPLC with U.V. detection at 320nm. 830.6302 Color White 830.6303 Physical State Granular powder hygroscopic; solid. 830.6304 Odor Odorless Stability to sunlight, normal Stable following storage at 54

## oc for 14 days, exposure to artificial daylight for 28 days, had no exothermic 830.6313 and elevated temperature, reaction or weight loss upon exposure to air at 150- metals/metal ions 160°C, no reaction with 10% iron, tin, or aluminum. Product has no oxidizing orreducing potential, based on 830.6314 Oxidation/Reduction: results ofexposure to water, monoammonium Chemical Incompatibility phosphate, iron powder, hydrogen peroxide, and kerosene. 830.6315 Flammability-Flash point Non-flammable. Flash Points: Not applicable. 830.6316 Explodability Product is not explosive (exposure to heat, mechanical shock, or friction did not cause the product to explode). 830.6317 Storage Stability Stable following storage for about 12 months. 830.6319 Miscibility Not apj>licable:_Q_roduct is a solid. 830.6320 Corrosion Characteristics Stable for at least 3 months. Not corrosive to packaging following storage for about 12 months. 830.6321 Dielectric breakdown Not applicable: product is a solid and is not intended for voltage use around electrical equipment. 830.7000 pH 6.62 at 19.8°C (for I% aqueous solution). 830

.7050 UV Nisible Absorption Not expected to absorb at A> 300 nm 830.7100 Viscosity Not applicable: product is a solid. 830.7200 Melting point >370°C (metal block method). 830.7220 Boiling point Not applicable: product is a solid. 830.7300 Density 2.429 g/cmj ; 2.4550 g/mL It dissociates in water to ammonium and bromide ions. 830.7370 Dissociation constant Ammonium bromide is a weak acid with a pKa of -5 in water.

Page 5 of 16OPPTS Physical and Chemical Value Guideline No. Properties 830.7550 Partition coefficient (n- Not applicable since NH4Br is inorganic salt. octanoVwater) 830.7840 Solubility in water 97 g /100 mL at 25°C in water. 830.7860 Solubility in organic Soluble in organic solvents

- alcohol, acetone, ether, solvents ammonia. 830.7950 Vaporpressure 9.8 X 10-7 mmHg Henry's law constant 1.3 X 10-13(Calculated) 

### Physical and Chemical Properties ofMonochloramine End use products ofammonium bromide are used in conjunction with an oxidant such as sodiumhypochlorite or chlorine gas to produce monochloramine biocide 

### in situ. Inorganic chloramines represent the stoichiometric reaction products resulting from the reaction ofchlorine and ammonia in water; namely monochloramine, dichloramine, and trichloramine (Figure 1). Monochloramine (NH2Cl), dichloramine (NHCh) and trichloramine (NCh) are produced by either adding chlorine to a solution containing ammonia, by adding ammonia to a solution containing free residual chlorine orby adding premixed solutions ofammonia and chlorine to water. However, the production ofmonochloramine versus dichloramine and trichloramine is highly dependent uponpH, the ratio ofchlorine to ammonia-nitrogen and, to a lesser extent, temperature and contact time. A pHbetween approximately 7.5 and 9.0 is optimum for the formation ofmonochloramine; the ideal pH is 8.3. ,,,N, H'''''J 

### 'CI 

### H Monochloramine (NH 2Cl) ,,,N, H'''''J 

### 'CI Cl Dichloramine (NHC/ 2 ) _......N•• 

# c1" \·····c1 Cl Trichloramine (NC/3) Figure 1. Chemical Structures ofInorganic Chloramines When ammoniumbromide inthe end use product reacts in a 1: 1 molar ratio sodium hypochlorite, a 12.5% aqueous solution of sodiumhypochlorite under controlled conditions forms a 12.5% solution ofmonochloramine. Monochloramine is the preferred form of chloramine in the industrial process system use for microbiocidal purposes. Summary of chemical and physical properties ofmonochloramine is presented inTable 5 (Source: Toxnet). 

### Table 5. Summary ofChemical and Physical Properties ofInorganicMonochloramine CHEMICAL 

### VALUES PARAME1ER CAS# 10599-90-3 Molecular Formula NH2Cl Molecular Weight 51.48 Page 6 of 16CHEMICAL VALUES PARAMETER Solid form: Colorless crystals Color/Physical State Liquid form: Yellow liquid Aqueous form: Colorless liquid Odor No data available Melting Point -66°C Itmay decompose violently above -66 deg °C BoilingPoint No data available Water Solubility Soluble Other solubilities ETOH, ether, CC14, benzene pH 

### ---- Density


### ----- Partition coefficients -1.19 Vapor pressure 1.16E-009 mm Hg at 25 °C (source: EPI Suite version 4.0) Henry's Law constant 7.857E-O 17 atm-m3 /mole (source: EPI Suite version 4.0) Monochloramine is oxidized by ozone faster than ammonia Other

Chemical/Physical Ultraviolet light depletes only free chlorine, whereas chloramines seem to be quite stable in Properties sunlight. Chloramine decay has been suggested to be at most 0.2 mg/litre per sunlight hour between 10 a.m. and 2 p.m. (latitude 30-40°N).


### B. Environmental Fate Summary A review oflabels indicate that in pulp and paper mills application ofammonium bromide as a disinfectant is done in a closed system, when 12.5% NaOCl or Clz (one label: EPA Registration Number 8622-76 indicates this process) is mixed with ammonium bromide. Inthis mixture solution there will be three reactants: bromide anions (BO, hypochlorite anions (OCr) and ammonium cations**(N~**+). An understanding ofbasic chemical reactions ofammonium bromide, ammonium, and bromine will help in understanding the unique environmental fate and transport ofammonium bromide. The stoichiometric reactions ofammonium bromide in the closed system feeder/delivery system in industrial process water systems is described below in two sections. One section examines the reactions ofbromine contained within ammonium bromide and the other the ammonium ion in the presence ofhypochlorous acid.

Page 7 of 16Stoichiometric Reactions ofBromine from Ammonium Bromide Use 

### The following chemical information is provided to understand the aqueous chemical processes. Ammonium bromide is an inorganic and an ionic chemical, and it undergoes very rapid reactions in the presence ofother inorganic species

. Inorganic ionic reactions are much faster than organic reactions, and understanding of these reactions is critical for the environmental fate processes. Ammonium bromide readily dissociates in water into the respective ammonium cations and bromide anions (bromine is in a -1 oxidation state):

Awunonium**d~** NH + 4 

### Equation 1
The bromide ion in the presence ofchlorine gas 

### (Ch) in solution readily undergoes a reaction to form bromine gas (bromine is in a zero oxidation state1) 

### and chloride anions: 

## + C l2 (aqueous)**~** 

## + Br2 (aqueous) 

### Equation 2**·o idt>**  a- nion Chlo rid;;**ar.~ion** 

### Bromine gas in an aqueous solution reacts with the water releasing bromide anions (bromine in 

### -1 oxidation state) and hypobromite (bromine in +1 oxidation state): Br2 (aqueous) 

## + H20 Hy pobr o m it;;**io ~t** **l** Eko1nids ion 

### Equation 3 Alternatively in the presence ofhypochlorite released from sodium hypochlorite in solution rather than from 

### Ch, bromide anions (bromine in -1 oxidation state) released from ammonium bromide form hypobromite (bromine in +1 

### oxidation state) and chloride anions:

Bromide anton H ypochlori tB a- nion H ypobromitt>**~ai ot** **~** 

### Equation4 ChioTid' ganao· n 

### In an aqueous solution hypobromite is in equilibrium with hypobromous acid orbromic acid (Equation provided below) which is a weak, unstable acid. Hypobromous acid has properties very similar to hypochlorous acid, and is used like hypochlorous acid as a bleach, an oxidizer, a deodorant, and a disinfectant. The percentbromine as the hypobromite anion versus hypobromous acid (HOBr) is a function ofpH as listed in Table 6.

HypobTom o · us o r Brom ic acid Hy d 1 •ogen ion Hypobr om ite ion 

### Equation 5

1 Oxidation state is a measure ofthe degree ofoxidation ofan atom which in turn represents the tendency to lose electrons present in the valence orbitals 

### Page 8 of 16

### Table 6. Percenthypobromite in solution as a function ofpH pH % 

### Bromine as Bro- % 

### Bromine as HOBr 6.0 0.0 100 6.5 0.6 99.4 7.0 2.0 98.0 7.5 6.0 94.0 8.0 17

.0 83.0 8.5 43.0 57.0



### . . 

### . . Source: http://www.lenntech.cornlprocesses/dtsmfecttonlchemtcalldtsmfects

-bromme

.htm 

### Table 6 indicates that ifthe is pH> 8 (alkaline medium) it makes the availability of hypobromite optimum, and also shifts the equilibrium toward hypobromite as it gets used up during a disinfection process. It 

### also helps in determining which pH will produce highest reactivity ofhypobromite ion orhypobromous aicd Hypobromite (bromine in +1 oxidation state) can further decompose where one mole of hypobromite reacts with two electrons to form bromide (bromine in -1 oxidation state). 

### 2e- 

## + = 

### Equation 6
Ammonium ions in the presence ofhypobromite (BrO-) may form monobromamine: Equation 7
Ifthis reaction is not controlled, the formation ofdibromamine, and tribromamine occurs. NH 2 Br 

## + HOBr**~** MHBr2 

## + H 20 

### Equation 8 M on ob 1 •om a€ne H ypol nro-mous Gcid Di ,br omGmin
- e W a t e·>" NHBr2 

## + HOG l ----7 NBr3 

## + H 20 

### Equation 9 Dibr omamin ll H yp ochlorous acid Trib· romaminli W B t8'1' 

### Alternatively, in a strongly alkaline solution (pH> 10 up to 14) the hypobromite anions canfurther undergo oxidation to form bromate anions (bromine in 

### + 7 oxidation state) and bromide anions, bromate is a strong oxidizing agent similar to chlorate: BrOs:- 

## + Equation 10 Hyp obrc m its- anio ns Eilr o n'l

.at e anioms BJ•om ide a ni o- ns 

### Given the application method and controlled conditions, formation ofbromate ions is considered unlikely for the registered uses ofammonium bromide. Released hypobromite in the system under consideration is expected to act as an oxidant releasing bromide ions.

Page 9 of 16This is supported by two studies conducted with bromide compounds, which while not using ammoniumbromide, still provide some insight into the formation ofbromate from bromide in solution. One study provides insight under different pH conditions and excess bromide, and the other excess bromide and sunlight in the presence ofhypochlorite. These consist ofa laboratory study conducted bythe United States Navy (A Memo from Timothy Leighton to Mark Hartman: Nov.3, 2005: SodiumBromide: Sodium Bromide: Residential and Dietary Antimicrobial Uses (Pools, Spas, Sugar Beets, and Fruit & Vegetable Wash). DP Barcode 321793)) with polybrominated trimethylbenzylammonium column, and the second study was a swimming pool monitoring study conducted with sodiumbromide, respectively

. A lab study conducted byregistrants and submitted as a 6(a)(2) (Same memo ofTimothy Leighton cited above) showed that in the pH range of4 to 7
.5 and buffered conditions bromide in the concentrationrange of0.5, 2 reacted inthe following way:

• No bromate was detected over the pH range of4-6 for 5 days at any ofthe bromide concentrations.
• However at pH 7 at the bromide level of5 ppm, bromate started forming from day 1 (6.7 11g bromate/L). At day 4 bromate concentrations reached 9.1!-lg/L, and remained at this level on day 5 (9.1!-lg/L). Thus a steady state was achieved on day 4. This shows that even in the absence ofan oxidant and sunlight there is a possibility ofbromate formation under the right condition (acidic and neutral pH, constant temp, and high buffer concentration)

. However, the bromate level reached (9

. 1!-lg/L or 0

.0091 mg!L) represents a 0

.002 fold conversion from the bromide to the bromated form which represents a very small conversion. The second study was conducted in the presence ofcalciumhypochlorite (Ca(OCl)z), sunlight, and a very high concentration of sodiumbromide (250 mg!L versus 6 mg!L, which is a permissible concentration for available bromine for swimming pool scenario) the conversion to bromate was as high as 3 ppm. It is clear that the formation ofhigher amounts ofbromate occurred underhighly exaggerated conditions. 

### Stoichiometric Reactions ofAmmonium from Ammonium Bromide Use In the presence ofhypochlorite (ClO

-) released from aqueous solutions ofhypochlorous acid, the ammonium ion released from ammoniumbromide (Equation 1) undergoes the following reaction: NH + 4 

## + Equation 11
Ifthis reaction is not controlled, the formation ofdichloramine, and trichloramine occurs.

Mon ochloram in e Hypo chlo-t •ous acid Dichl
- olt

·amin e Water Equation 12

Page 10 of 16NHC1 2 

## + HOC'l Equation 13 Dicldorami.11-111 Hypochlorous acid T-rich lora-mine Water The controlled conditions ofthe system used for paper and pulp (pH> 8, constant temperature, and molar ratios ofammonium ions and hypochlorite, will not likely produce dichloro and trichloroamines.


### Environmental Fate ofAmmonia Bromide Reaction Products Hypobromite and monobromamine have a similar capability to act as mild disinfectants like hypochlorite and monochloramine; so theoretically in the closed system ofammonium bromide and sodium hypochlorite, at an appropriate pH, many disinfecting moieties are likely be present. The three most likely chemicals formed in the feeder/delivery systemunder controlled conditions are: hypochlorous acid (or hypochlorite), hypobromous acid (or hypobromite ion), and monochloramine. These chemicals are inorganics so conventional fate studies do not apply. These chemicals have a tendency to form various intermediates depending on the pH ofthe system and the concentration ofthe various species involved. Unlike reactions with organics, typically inorganic reactions are much faster, and therefore not easy to keep tract ofthe intermediates. These intermediates cannot be classified as degradates in the classical sense. A study in simulated natural waters (MRID #452052-03) was conducted in lieu ofthe conventional hydrolysis study in simulated natural water at different pHs. The study was based onthe OECD Test Guideline 111, and included the following modifications: • Secondary effluent collected from a wastewater treatment facility was used; • The study was conducted at pH 7.7; and • Monochloramine was used as a reference material instead ofanother substance (aspirin) suggested in the test guidelines. Ammoniumbromide formed HOBr, and its decay as well as the decay ofchloramines was followed at two temperatures: 25 and 35 °C and also two concentrations ofFuzzicide were selected: expressed as 5.0 milligrams ofchlorine residual per liter (mg Ch/L) and 0.50 mg Ch/L; a first order kinetics was assumed inboth cases. Maximum halflife ofFuzzicide was 48 hours (2 days) and maximumhalflife for chloramine was 155 hours(> 6 days). Hence both ofthem degrade fast in the simulated natural water systems. The study did not mention the formation and likely presence ofBro-. However, ammonium bromide or its active moieties formed during the use and application are not stable and convert into other moieties and perhaps mineralize. However, this study shows that monochloramine under environmental conditions is not stable and undergoes rapid degradation in natural waters. For chloramine taking into account the physicochemical properties, and environmental fate parameters the source primarily from EPI Suite (version 4.0) a screening level environmental fate assessment summarized as follows:

Page 11 of 16

### • Monochloramine is highly soluble in water and its vapor pressure and Henry's Law Constant are both low. Therefore, it is not expected to volatilize from water surfaces quickly. • Its low Koc indicates that it is mobile in soils and sediments. • Its half-life in aqueous media varies from a fraction ofa day to about 40 days. (Health Canada, 1998), depending upon temperature, pH, and salinity. This study and other Canadian studies for aqueous medium decay ofchloramines show that in deionized water and seawater mixtures the halflife varied from 0

.68 days to 0.98 days. However, see below for a more recent observation. • A Canadian study onthe sediment ofGrand River, in North Saskatchewan River and Downes Creek showed the halflife of 1.4, 2.5 and 0.05 days. • No concrete studies are known thatprovides data onthe dissipation rate of chloramines from soil surfaces. • Monochloramine has been in use as a secondary disinfectant in the U.S. and internationally for over fifty years. Compared to hypochlorite ion, it degrades slowly and, hence, its disinfecting power in aqueous media is higher than hypochlorite. • All EPI Suite BioWIN (EPI Suite 4.0) models estimate that monochloramine is quickly biodegraded and it can be classified as readily biodegradable. (EPI suite classifies it fast biodegradation, which is less than a day) • PMRA in its most recent Proposed Registration Decision (March 2012)21 

### on Ammoniumbromide (Fuzzicide) has shown that monochloramine (referred to as bromide activated chloramine(BAC)) hydrolyses in water quickly and at pH 5 the halflife is 15.9 minutes, while at pH 9, the halflife was measured at 184 hours (12 days).

• Pulp and paper use ofammonium bromide (and monochloramine) as the active is used in a closed system, and the waste from this process is kept in holding ponds (in some registered labels). Thus the release waste to the wastewater streams is not likely to contain monochloramine keeping in view ofthe physical/chemical characteristics ofmonochloramine (short hydrolytic halflife, readily biodegradable etc.) • Similarly from the recirculating cooling tower process, the waste is not likely to contain monochloramine. Chloramine in Drinking Water: Since it is used as a secondary disinfectant for waste water treatment, chloramine is likely to be found as a contaminant in drinking water. EPA has set a maximum Drinking Water Limit for a number ofcontaminants in surface water (and in drinking water) regardless ofthe source. The maximum contaminant limit goal (MCLG) for chloramines is 4.0 ppm and the maximum residual disinfectant level goal (MRDLG) is also 4.0 ppm. Thus most ofthe water utilities are required to keep the level ofchloramines at this level for residential drinking water.

2 Pmra.publications@hc-sc.gc

.ca 

### Page 12 of 16

### Water Quality Ammoniumbromide is not identified as a cause ofimpairment for any water bodies listed as impaired under section 303(d) ofthe CleanWater Act, based on information provided at the Agency's National Pesticides Cause ofImpairment ofWaters website (searched August 27, 2012l In addition, no Total Maximum Daily Loads (TMDL) have been developed for ammonium bromide, based on information provided at the Agency's National Pesticide TMDL web site (searched August 27, 2012)4

. More information on impaired water bodies and TMDLs can be found at http://www.epa.gov/owow/tmdl/

. The Agency invites submission ofwater quality data for this pesticide. To the extent possible, data should conform to the quality standards in Appendix A ofthe 

### OPP Standard Operating Procedure: Inclusion of Impaired WaterBody and Other Water Quality Data in OPP's RegistrationReviewRiskAssessmentand Management Process (see: http://www.epa.gov/oppfeadl/cb/ppdc/2006/november06/session1- sop.pdf), in order to ensure they can be used quantitatively or qualitatively inpesticide risk assessments. 

### C. Ecological Effects Summary All ofthe major oxidants formed in the registered application method of ammonia bromide would be measured as chlorine residual: chloramines, bromamines, hypochlorite, hypobromite. The AmbientWater Quality Criteria for Chlorine- 1984 document contains a review ofpublic literature on effects ofchlorine (total residual chlorine) and based onthe data derives freshwater and saltwater organism acute and chronic water quality criteria as total chlorine residual. Current ambient water quality criteria for chlorine ortotal chlorine residual are based on the data in the 1984 document and the method for deriving water quality standards discussed in a 1986 Water Quality Document (USEPA, 1986). • Freshwater Criterion Maximum Concentration= 19 J.lg/L; • Freshwater Criterion Continuous Concentration = 11 J.lg/L; • Saltwater Criterion Maximum Concentration= 13 J.lg/L; and • Saltwater Criterion Continuous Concentration= 7.5 J.lg/L A review oftoxicity effects data for ammonium bromide and for monochloramine is summarized in the following sections. No ecological risk assessment has previously been performed for ammonium bromide.


### a. Toxicity to Terrestrial Animals The available toxicity studies submitted by the registrant categorize ammonium bromide TGAI as being practically nontoxic to birds (Table 7). Mammalian toxicity data are presented in the Human Health scoping document. No additional data are required for terrestrial animals.

3

. http://iaspub.epa.gov/tmdl waters 10/attains nation cy.cause detail 303d?p cause group id=885 4 http://iaspub.epa.gov/tmdl waterslO/attains nation.tmdl pollutant detail?p pollutant group id=885&p pollutant group name=PESTICIDES Page 13 of 16

### Table 7. Summary ofthe Endpoints from Submitted Terrestrial Ecotoxicity Studies for the TGAI Study Type Species Testmaterial Toxicity Toxicity MRID& Classification Status Acute- Mallard Ammonium bromide LD50: >2000 Practically 447213-01 Avian Oral (Anas mg/kg-bw/day

850.2100 platyrhynchos) (98.5% ai) nontoxic AcceptableAcuteAvian Mallard Ammonium bromide LC50: >5000 ppm Practically 447213-02 Dietary (98.5% ai) nontoxic Acceptable 850

.2200 

### b. Toxicity to Aquatic Animals The available toxicity studies submitted by the registrant categorize monochloramine (generated from ammonium bromide mixed with sodium hypochlorite) as being acutely highly to very highly toxic to freshwater and estuarine/marine animals (Table 8). No additional acute toxicity data are needed. Because monochloramine is so acutely toxic, sublethal reproductive effects are not expected. Chronic toxicity data are not required. 

### Table 8. Summary ofEndpoints from Submitted Fish and Aquatic Invertebrate Ecotoxicity Studies for Monochloramine. Study Type Species Test material Toxicity Value Toxicity Classification Rainbow trout Very highly (Oncorhynchus Ammonium 96-hr LC50: 58 jlg Cl2/L my kiss) bromide toxicAcuteFreshwaterFish (99.9% ai) 850.1075 Bluegill sunfish in 10% (Lepomis hypochlorite 96-hr LC5o: 290 jlg Ch/L Highly toxic macrochirus) solution with carbonate buffer Acute- Sheepshead Estuarine/marine minnow Highly toxic Fish (Cyprinodon 96-hr LC50: 360 jlg Cl2 /L 850.1075 variegatus)AcuteFreshwater Water flea 48-hr EC5a: 23 jlg Ch/L Very highly Invertebrate toxic

850.1010 Acute- Mysid Estuarine/marine Very highly Invertebrate (Mysidopsis 96-h LC5o: 36 jlg Ch/L toxic

850.1035 bahia) Acute- Eastern oyster Estuarine/marine Very highly Invertebrate (Crassostrea 96-h EC50: 18 jlg Cl2/L toxic

850

. 1025 virginica)



### Page 14 of 16 MRID& Status 447213-13 Acceptable
447213-12 Acceptable

447213-16 Acceptable

447213-14 Acceptable

447213-15 Acceptable

447213-17 Acceptablec. Toxicity to Aquatic Plants A summary ofacute aquatic ecotoxicity data endpoints from two registrant-submitted studies is provided in Table 9. Table 9. Summary ofthe Endpoints from Submitted Aquatic Plant Ecotoxicity Studies for Monochloramine.

Study Type Species Test material Toxicity Toxicity MRID& Classification Status Aquatic Plants- Duckweed Ammonium bromide 7-day EC5o: 680 Jlg nla 452052-02 Vascular (Lemna gibba) (99.9% ai) Cl2 /L Acceptable 850.4400 Aquatic in 3% hypochlorite Plants- Green algae solution with 452052-01 Nonvascular (Pseudokirchneriella carbonate buffer 72-h EC50: 28 Jlg Clz/L nla Acceptable

850.5400 subcapitata) d. Aerobic Microbial Inhibition AnActivated Sludge Respiration Inhibition (ASRI) (MRID#452052-04) study was conducted using OECD Test Guideline 209 with an activated sludge obtained from a domestic waste site. The study serves two purposes: a) a screen to determine ifthe pesticide will adversely affect aerobic microbial treatment plants; b) determine the level ofnon-inhibitory concentration ofthe pesticide which in turn canbe used for a biodegradability test. Test solutions were made by mixing ammoniumbromide and sodium hypochlorite along with the reference material (3,5-dichlorophenol). A log plot of sample concentrations versus the oxygen consumption yielded an ICso value of 16 mg/L, which was well within the 5 to 30 mg/L value. This limit indicates that the actives do not adversely affect the microbial population in the wastewater system.
Environmental Fate and Ecotoxicity Data Gaps and Anticipated Work There are no ecological effects data gaps for ammonium bromide or its reaction product, monochloramine. For environmental fate, a hydrolysis study in open literature was identified for monochloramine. The Agency requires registrants to formally submit the hydrolysis study to the Agency; therefore, the Agency anticipates the need to call-in a hydrolysis study

. The Agency has concluded that environmental exposure from these chemical substances is not likely to occur in the aquatic environment due to registered uses as labeled. Therefore, an ecological risk assessment is not anticipated to be needed. 835.2120- Hydrolysis

Page 15 of 16Endangered Species Determination Based onthe ammonium bromide use pattern, rapid and complete formation of monochloramine under controlled application conditions, the rapid hydrolysis and biodegradation ofmonochloramine in industrial water systems, including their waste systems, the Agency anticipates the registered uses will have "no effect" on endangered orthreatened terrestrial or aquatic species, or their designated critical habitats, as listed by the USFWS and the NOAA. However, the Agency will review any comments madeby the public on this document and will conduct an environmental risk assessment ifnew information warrants such action. An ecological risk assessment planned during registration review allows the Agency to determine whether an antimicrobial pesticide's use has "no effect" or "may affect" federally listed threatened or endangered species (listed species) or their designated 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 Service (the Services), as appropriate.

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