SUBJECT:

FROM:

THRU:

TO: UNITED STATES ENVIRONMENTAL PROTECTIONAGENCY WASHINGTON D.C., 20460

OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION September24, 2012 Product Chemistry, Environmental Fate, and Ecological Effects Scoping Document in SupportofRegistration Review ofAmmonia and Ammonium Sulfate

PC Codes: DP Barcodes: Ammonia: 005302 Ammonia: 404902 Ammonium sulfate: 005601 Ammonium sulfate: 401476 DecisionNos.: Registration Nos.: See Table 1 Ammonia: 469069 Ammonium sulfate: 464385 PetitionNo(s)

.: NA RegulatoryAction: Ecological Environmental ScopingDocument for Registration Review RiskAssessmentType: Single chemical Case Nos

.: Ammonia: 7440 Ammonium sulfate: 5073 TXRNo.:NA CAS Nos.: Ammonia: 7664-41-7 Ammonium sulfate: 7783-20-2 MRID Nos.: See Tables 7. 11, 12 & 13 40 CFR: None Srinivas Gowda, M.S. Microbiologist/Science**Coordinator~ 2r1'~v** **~ ~**  William Erickson, Ph.D., BiologistitA":

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

### .n**JktU~v---J** RiskAssessment and Science SupportBranch (RASSB) Antimicrobials Division (7510P)

. .**~** StevenWeiss, Acting Branch Chief 

# %c
DonnaRandall, M.S. Ecological Risk AssessmentTeam Leader Risk Assessment and Science Support Branch (RASSB) Antimicrobials Division (7510P) Rebeccavon dem Hagen, Chemical ReviewManager Regulatory Management Branch II Antimicrobials Division (751OP)

Page 1of 23Executive Summary Ammonia and ammonium sulfate are inorganic nitrogen compounds which are used on site to produce the oxidant and microbiocide, monochloramine, under controlled application conditions. Ammoniabromide is another inorganic nitrogen, ammonium salt compound that produces the oxidant and microbiocide, monochloramine, butit also produces hypobromous acid, another inorganic oxidant, so the Registration Review for ammoniumbromide is addressed separately (Case Number 5002). Ammonia and ammonia sulfate are registered for use as microbiocides for controlling algal, bacterial and fungal deposits (slimes) in influent water systems, and all process water systems used for the manufacture ofpaper and paperboard products (food contact) and in industrial cooling towers, recirculating cooling water systems, evaporative condensers, brewery and food pasteurizers, industrial fresh water systems, air washers, seawater desalination and reverse osmosis systems, paint spraybooth sumps, non-fish containing decorative fountains and ponds used for cooling purposes, and sewage and wastewater systems. They are also registered for the control ofalgae, bacteria, fungi and mollusks in both seawater and freshwater influent systems. The manufacturing and end use products have a declared ammonia content of7.59% total ammonia1or a declared ammonium sulfate content ranging from 20% to 28% which is equivalentto a total ammonia (ammonia plus ammonium expressed as ionized ammonia) contentranging from 5.45% to 7.59%. The end use products are used in conjunction with an oxidant sodiumhypochlorite (12.5-15%) to produce monochloramine. The Agency is conducting its fate and environmental assessment onthe monochloramine formed during the application. The active ingredient ammonium sulfate is a strong oxidizing agent, the formation of monochloramine provides a slower acting, less aggressive oxidizing agent and biocide. The active ingredient ammonium sulfatehas no pesticidal activity per se. The actual biocide, monochloramine is produced on-sitebyreacting the registered products with sodium hypochlorite. The monochloramine is generated and fed into water process systems using closed, automatic dosing/metering systems. Ammonium sulfate is reacted with an aqueous solution ofsodium hypochlorite (1.0-1.5 to 1 molar ratio ofammonia and hypochlorite) under alkaline (pH ;:::8.5) conditions, as specified by some labels, to form monochloraminerather than a mixture ofmono-, di-, and trichloramines. Monochloramine is added to the water to betreated immediately as it is formed. On one label, when theproduct is used to treat once-through industrial water system reduction ofchloramine using sodium metabisulfite is required before discharge for effluents from these uses. Aqueous Ammonia was first registered in USA in 1971 for conventional uses. Itwas first registered as a microbiocide for use inpulp and paperboard process water systems in 2007. There are currently two active products, one ofwhich is for formulation use only and the other is an end use productboth have a declared total ammonia content of7.59% which is equivalent to an ammonia sulfate content of28%. Conventional uses are no longer active. Ammonium sulfate was first registered in the United States in 1987 for wood preservative uses. In 2011 two end-use ammonium sulfateproducts, Nalco 60620 and Fennosurf 586 were registered byNalco Company and Kemira Chemicals, Inc., respectively for use in pulp

1 Sum ofun-ionized and ionized ammonia content expressed as ionized ammonia. Page 2 of23and papermill water systems to control bacteria, algae and fungi. There are currentlytwo active end use products, the declared ammonium sulfate content ofone is 20% and the other is 28%. Use as a wood preservative is no longer active. Conventional fate data cannotbe generated for aqueous ammonia, ammonium sulfate, and monochloramine as these are inorganic species. The environmental fate ofthese compounds is complex but is knownbased primarily oninorganic and oxidation/reduction chemistry. More recent fate datahas established that monochloramine is not stable inthe environmental media; it is considered biodegradable in water, and in sediments and possibly in soils. OPP's mostrecent exposure assessment (EPA 2011), conducting for the registration ofthe Nalco ammonium sulfate product, identified that the pulp and paper water use would not likely result in exposure or minimal exposure because of the reactivity ofchloramine and retention ofdischarge water in holding ponds where any unreacted chloramine will react with organic matterpriorto any release into the aquatic environment. However, there is uncertainty for once through industrial water system uses whetherthere is sufficienttime for chloramine to dissipate completelybeforebeing discharged to surface waters. A field dissipation study is needed to refine exposure estimates and address this uncertainty. Ammonium sulfate is at most only moderately toxic to birds. Monochloramine generated from combining ammonium sulfate solution with sodiumhypochlorite is highly to veryhighly toxic to aquatic plants and animals. These monochloramine data will beused to supportthe monochloramine requirements for ammonium sulfateuses. In addition to the available data, the following monochloramine environmental fate and ecological effects data are needed to conduct a risk assessment for once-through industrial water systems: aquatic field dissipation, chronic data for an estuarine/marine fish and shrimp species, chronic freshwater fish and invertebrate data, Tier II (dose response) seedling emergence- rice data, and aquatic plant growth (algal) Tier II (doseresponse) data for a marine diatom, freshwater diatom, and a blue-green algae. Environmental fate and ecological effects risk assessments, including an endangered species assessment, are anticipated to be conducted for the once-through industrial water systems. Introduction Ammonia and ammonium sulfate are inorganic nitrogen compounds registered for use as microbiocides for controlling algal, bacterial and fungal deposits (slimes) in influent water systems, and all process water systems used for the manufacture ofpaper and paperboard products (food contact) and in industrial cooling towers, recirculating cooling water systems, evaporative condensers, brewery and food pasteurizers, industrial fresh water systems, air washers, seawater desalination and reverse osmosis systems, paint spraybooth sumps, non-fish containing decorative fountains and ponds used for cooling purposes, and sewage and wastewater systems. They are also registered for the control ofalgae, bacteria, fungi and mollusks in both seawater and freshwater influent systems. Ammonia and ammonium sulfate are used on-site in conjunction with sodiumhypochloriteto produce the microbiocide, monochloramine within approved closed, feeder/delivery systems. Solution produced bythe delivery system is immediately added to the process waters for which treatment is required.

Page 3 of23Monochloramine is a slower-acting, less aggressive, oxidizing microbiocide than ammonia. The label requires trained personnel operate the system to maintain residual levels. Ammonia bromide is another inorganic nitrogen, ammonium salt compound that produces the oxidant and microbiocide, monochloramine, but it also produces hypobromous acid, another inorganic oxidant, so the Registration Review for ammoniumbromide is addressed separately (Case Number 5002). Aqueous Ammonia was first registered in USA in 1971 for conventional uses. Itwas first registered as a microbiocide for use in pulp and paperboard process water systems in 2007. There are currently two active products, one ofwhich is for formulation use only and the other is an end use productbothhave a declared total ammonia2 content of7.59% which is equivalent to an ammonia sulfate content of28% (Table 1). Conventional uses are no longer active. A 1.0- 1.5: 1 molar ratio ofthe end use product to sodiumhypochlorite is mixedto produce monochloramine. The solution is applied at a rate to obtain at least 1to 2 ppm in excess of system oxidant demand (maximum of5 ppm) measured as total chlorine in the process water. Whenthis product is used to treat sewage and wastewater systems, seawater, and freshwater influent systems for once-through industrial water systems, and seawater desalination and reverse osmosis systems, and the system water is not sent to a POTW, residual levels of chloramine in the effluent mustbe monitored and neutralized using on-line monitoring and control equipment. Detailed information on these registered products is provided in Table 1 and 2. Ammonium sulfate was first registered in the United States in 1987 for wood preservative uses. In 2011 two end-use ammonium sulfate products, Nalco 60620 and Fennosurf 586 were registeredbyNalco Company and Kemira Chemicals, Inc., respectively for use in pulp and paper mill water systems to control bacteria, algae and fungi. There are currently two active end useproducts, the declared ammonium sulfate content ofone is 20% and the other is 28%. Use as a wood preservative is no longer active. Detailed information on these registered products is provided in Table 1 and 2. The Nalco product is blended to achieve an approximate a molar ratio of 1.0-1.2 to 1.0 ofNalco 60620 to sodiumhypochlorite (12.5%) to produce monochloramine on-site. The label requires the design, treatment, installation, calibration, and operation ofthe feeding system in all plants to be conducted only by authorized and trained personnel. TheFennosurf586 (Kemira Chemicals, Inc.) product is blended to a minimum molar ratio of 1.5:1.0 product to sodium hypochlorite. A Reregistration EligibilityDecision (RED) was not issuedbythe Agencyfor ammonium sulfate because the initial registration date was after the November 1984, federal mandated cutofffor initiation ofthe RED process. An ecological risk screening assessment for cooling towers was conducted in 2008 (EPA 2008), and concluded that listed and nonlisted aquatic organisms may be at risk from exposure to monochloramine released from cooling towers, but additional data were needed to refine the assessment. Ecological risk for pulp and paperuse was recently assessed bythe Antimicrobials Division (EPA 2011). That assessment concluded minimal acute or chronic risks for listed and nonlisted species. Exposure was presumed to be minimal based onreactivity in the system and retention ofdischarge water in

2 Sum ofun-ionized and ionized ammonia contentexpressed as ionized ammonia. Page4 of23holding ponds where it is expectedto react with organic matter prior to any release ofthe holding pond water into an aquatic environment. Table 1. Registered Products ofAmmonia and Ammonium Sulfate EPA Product Company Active Ingredient Active Ingredient Registration Name Name Listed on Label

- Expressed as Percent

Number Percent A.l. A.l. Ammonium Sulfate 9386-49 Fennosurf586 Kemira Ammonia (total) 1

- 7.59% Ammonium Sulfate- 28% 2 Chemicals, Inc. 1706-240 Nalco 60620 Nalco Ammonium Sulfate- 20% Ammonium Sulfate- 20% Company Buckman 1448-433 Busan 1215 Laboratories, Ammonia (total) 1-7.59% Ammonium Sulfate- 28% 2 Inc. Buckman 1448-432 BCMW Laboratories, Ammonia (total) 1-7.59% Ammonium Sulfate- 28% 2 Inc

. 1Total Ammonia (un-ionized ammonia (NH3) plus ammonium (NH/) content) as expressed as ionized ammonia (NH/)

. 2 Conversion oftotal ammonia expressed as ionized ammonia content to ammonium sulfate equivalent content: (7

.59gas NH4

### +) X (1 mole NH4

### +) X (1 mole (NH4)zS04) X ( 132 g (NH4)zS04 ) 

### = ZS% 100g ofSolution 18g NH4+ 2 mole NH4+ 1 mole (NH4)2S04

Page 5 of23

### Table 2. Ammonia and Ammonium Sulfate Antimicrobial Use Summary
Use Site (TreatmentSite) Application Application Notes Method1 Rate IndustrialProcesses andWaterSystems Industrial cooling towers, 

## I recirculating cooling water I r systems, evaporative Nonauthorized, nontrained personnel condensers, influent water cannot operate system systems (freshwater and Residual levels ofchloramine in the seawater), brewery and food Metering 0.5-5.0 ppm of effluent from treated sewage and pasteurizers, industrial fresh (Enclosed residual oxidant water systems, air washers, feeder/ demand in wastewater systems, seawater, and seawaterdesalination and delivery process or freshwater influent systems for oncereverse osmosis systems, paint system) water system2 through industrial water systems, and seawater desalination and reverse spray booth sumps, non-fish osmosis systems, where the system containing decorative water is not sent to a POTW, must be fountains and ponds usedfor monitored and neutralized. cooling purposes, sewage and wastewater systems Pulg and PagerBoard Metering I Systems: Influent water (Enclosed systems (fresh and sea) and all feeder/ process water systems usedfor delivery the manufacturer ofpaper and system): paperboard products that Slug feed 0.5-10 ppm of contact food including method; residual oxidant Nonauthorized, nontrained personnel associated cooling water Intermittent demand in systems and wastewater feed method; process or cannot operate system treatment systems, pulp, paper Continuous water system2 and paper board mill systems, feed method; nonpotable water systems, operated atpH starch slurries, and other >8.5 for process water that may contact OxiPro,**~12** food for Fennosurf
1Product is applied in conjunction with sodium hypochlorite. 2While the amount ofammonia and ammonia sulfate end use product and sodiumhypochlorite solution to add to the feeder box is listed onthe label, the amount actually appliedper 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
Chemical identity and the physical and chemical properties ofthe ammonium sulfate technical grade (TGAI) are provided in Tables 3 and 4. The primary source ofinformation for this assessment wasAmmonium sulfateMSDS Science Lab and OECD SIDS October2004.

Page 6 of23

### T bl 3 Ch ' Ild 

### t't a e 

# . em1ca en l[Y 

### Ammonium Sulfate TGAI (> 99 %) Chemical Narne Ammonium sulfate Common Name Ammonium sulfate Diammonium sulfate, Synonyms Diammonium sulphate, Mascagnite, Sulfuric acid, diammonium salt Classification Inorganic Sulfate PC Code 005601 CAS No. 7783-20-2 Molecular Formula NzHsS04 (NH4)zS04 Molecular Weight 132.14 g/mol 0 

## o- f\JH+**~/** 4 Molecular Structure: 

## s

# ~' NH+ 

## o o- 4 Ammonium sulfate


### Table 4. Product ChemistryData Summary OPPTS Physical and Chemical Guideline Ammonium sulfate TGAI (> 99 %) No. Properties

830.1550 Product identity and Referto Table 3. composition 830.1800 Enforcement analytical method Titration method 830.6302 Color White crystals, granules orpowder. White orbrown orthorhombic crystals 830.6303 Physical State crystals and lumps 830.6304 Odor Odorless Stability to sunlight, normal and 830.6313 elevated temperature, Stable. metals/metal ions Oxidation/Reduction: Chemical Contact with strong oxidizers may cause fire or 830.6314 Incompatibility explosion. Incompatible with strong bases. Highly reactive with oxidizing agents. Reactive with alkalis. May becombustible athightemperature. Flammable in 830.6315 Flammability-Flash point presence ofoxidizing materials. Slightly flammable to flammable in presence ofheat. Flash point: > 200 °F. 830.6316 Explodability Explosive in presence ofoxidizing materials 830.6317 Storage Stability Stable under normal conditions ofuse and storage. 830.6319 Miscibility Not applicable. The product is not an emulsifiable liquid. Com_IJletely miscible in water.
Page 7 of23OPPTS Physical and Chemical Guideline Ammonium sulfate TGAI (> 99 %) No. Properties 830.6320 Corrosion Characteristics Does not attack iron or aluminum I Ammoniacal solutions. Non-corrosive in presence ofglass. 830.6321 Dielectric breakdown voltage Not applicable. This product is an inorganic salt solution, not intended for use around electrical equipment. 830.7000 pH 5.5 (0.1 M aqueous solution). 5-6 (5% soln.) 830.7050 UVNisible**Abs~q>tion** Does not adsorb in the UV-visible range. 830.7100 Viscosity_ NA. 830.7200 Melting point > 280 °C (decomposes) 830.7220 Boiling point Solid. Decomposes before boiling. Decomposes upon heating above 250°C. 830.7300 Density 1

.77 g/mL at 25 

## oc 830.7370 Dissociation Constant In aqueous media, ammonium sulfate dissociates in to ammonium and sulfate ions (NH/, SO/). 830.7550 Partition coefficient (n- Not applicable

. Itis an inorganic salt. octanollwater) 830.7840 Solubility in water 767 g/Lat 25 °C 830.xxxx Solubility in organic solvents Insoluble in acetone, ethanol, and ether 830

.7950 Vaporpressure 6.63E-022 mm Hg (EPI Suite version 4.0)

- Non-volatile Henry's Law Constant 3.278E-027 atm-mj/mole (EPI Suite version 4.0).


### Physical and ChemicalProperties of

### Monochloramines
End use products ofammonia and ammonium sulfate are used in conjunction with sodium hypochlorite to produce monochloramine biocide 

### in situ. Inorganic chloramines represent the stoichiometricreactionproducts resulting from the reaction ofchlorine and ammonia in water; namely monochloramine, dichloramine, and trichloramine (Figure 1). Monochloramine (NH2Cl), dichloramine (NHCh) and trichloramine (NCb) are producedby either adding chlorineto 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 andtrichloramine is highly dependentupon pH, theratio ofchlorine to ammonia-nitrogen and, to a lesser extent, temperature and contacttime. According to available literature, a pHbetween approximately7.5 and 9

.0 is optimum for the formation ofmonochloramine; the ideal pH is 8.3.

Monochloramine 

### ,,,N....._ H'''''

# I "'CI Cl Dichloramine _,..N,, 

## cr' \ ·····c1 Cl Trichloramine Figure 1. Chemical Structures ofInorganic Chloramines

Page 8 of23When ammonium from ammonia and ammonium salt in the end use products reacts in 1.0-1.5:1.0 molarratio ofproduct to a 12.5% aqueous solution ofsodiumhypochlorite, monochloramine is formed. Monochloramine is the preferred and expected form ofchloramine in the industrial process systemuse for microbiocidal purposes. Summary ofchemical and physical properties ofmonochloramine is presented in Table 5 (Source: Toxnet and EPI Suite v.4.0). 

### Table 5. Summary ofChemical and Physical Properties ofInorganicMonochloramine Chemical VALUES Parameter CAS# 10599-90-3 MolecularFormula NH2Cl MolecularWeight 51.48 Solid form: Colorless crystals Color/Physical State Liquid form: Yellow liquid Aqueous form: Colorless liquid Odor No data available Melting Point -66°C It may decompose violently above -66 °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'sLaw 7.857E-017 atm-m3 /mole (source: EPI Suite version 4.0) constant Monochloramine is oxidized by ozone faster than ammonia Other Chemical/Physical Ultraviolet light depletes only free chlorine, whereas chloramines seem to be quite Properties stable in sunlight. Chloramine decay has been suggested to be at most 0.2 mg/liter per sunlight hour between 10 a.m. and 2 p.m. (latitude 30--40°N).



### B. Environmental Fate Summary Ammonia, as aqueous ammonia, and ammonium sulfate are registered for use as: a bactericide, bacteriostat, and microbicide. TheAgency is presenting this scoping document on ammonia in solution, ammonium sulfate and monochloramine. Some chemical reactions are included to explain the chemistry ofthe products, and ammonium ion derived chemicals like monochloramine.

Page 9 of23The central atom in ammonium ions and monochloramine is nitrogen. Nitrogen is a versatile element which forms compounds in various oxidation states from -3 to+ 5. Inorder to understand the fate chemistry ofammonium ions and monochloramine, it is important to know the basic chemistry ofammonia. Thebasic stoichoimetric reactions ofammonia in water and ammonia or ammonium sulfate with sodiumhypochlorite in the closed system feeder/delivery system in industrial process water systems are described below. Basic Chemical Reactions ofAmmonia and Ammonium Ions Ammonia (NH3) is a gas at room temperature, and is manufactured on a large scale as a liquid (liquid ammonia) at high pressure and reduced temperature. Itis highly soluble in water butit actually reacts with water to form ammonium hydroxide:
H20**~** NH40H Equation 1 Ammonia Water Ammonium hydroxide which intum dissociates into:

Ammonium hydroxide Ammonium cation Hydroxide anion Equation 2
Reaction 2 is driven toward ammonium hydroxide and not toward ammonium ion and hydroxide ions. But as ammonium ions get removed inother chemical reactions, more ammoniumhydroxide dissociates and so on. Aqueous solutions in reaction systems 1 and 2 are basic solutions. Ammonium ion is the only composite 'cation ion' (positively charged); all other cation ions are basically metal ions. Combining Equation 1 and Equation 2 and adjusting the water and hydroxide ion to allow expression in terms ofthe hydronium ion (log ofthe inverse concentration is solution pH) provides a way to determine the ratio between the un-ionized ammonia and ionized ammonia when the pH ofa solution is known. Knowing the portion ofunionized ammonia to ionized ammonia is important for both understanding which way reactions with ammonia are likely to occur and aquatic toxicity.

Ammonia Hydronium ion Ammonium ion Water Equation 3
EPA's Draft2009Ambient Water Quality Criteria document (EPA 2009) states the following: "The chemical form ofammonia in water consists oftwo species, the more abundant of which is the ammonium ion**(N~**+) and the less abundant ofwhich is the non-dissociated orun-ionized ammonia (NH3) molecule; the ratio ofthese species in a given aqueous solution is dependent uponboth pH and temperature. Ingeneral, the ratio ofun-ionized ammonia to ammonium ion infresh water increases by 10-fold for each rise ofa single pHunit, and by approximately 2-fold for each 10 °C rise in temperature from 0-30° C.

Page 10 of23Table 6 below provides an example ofthe percent ofun-ionized and ionized ammonia content at 20 °C. For aquatic organisms, the un-ionized ammonia contenthas been found to be mostpredictive ofammonia toxicity. 

### T bl 6 P

a e 

# . t f 

### ercen o f t' 

### ammomum Ions as unc Ion o pJ a %ofTotal Ammonia as: pH Un-ionized Ammonia (NH3) 

### Ionized Ammonia**(N~**+) 6.5 0.125 99.875 7.0 0.395 99.605 7.5 1.239 98.761 7.7 1.95 98.05 8.0 3.81 96.190 8.5 11.15 88.85

.. Source: www.theaguanumwtki.com/Ammoma; AD amended table by addmg 10mzed ammoma content Note: There is a ten-fold increase in un-ionized ammonia content for a single rise in pHunit (e.g., at pH 6.5 unionized ammonia content is 0.125 and at pH7.5 it is 1.239 which is approximately 10 times higher). Like other cations, ammonium ion is a reactive species, and reacts with many anions like chloride, bromide, sulfate, nitrate 

### etc. to form salts

. Hence all ammonium salts are 'ionic' in nature, that is, they will dissociate into cations and anions. The dissociation equation ofconcern for ammonium sulfate is provided in Equation 4. Forregistered ammonia and ammonium sulfate uses the primary reactions ofconcern are Equations 1, 2, 3, and 4.



### + Equation 4 Ammonium ion Sulfate anion Ammonium sulfate Most ofthe compounds ammonium ion form are ionic in nature; however some substitutionreactions on ammonium do result in covalent compounds like monochloramine, dichloramine 

### etc. 

### StoichiometricReactions ofAmmonium from Ammonia and Ammonium Sulfate Use
In the presence ofhypochlorite (ClO-) released from aqueous solutions ofhypochlorous acid, the ammonium ionreleased from ammonia or ammonium sulfate (Equations 3 and 4) undergoes the following reaction:

Ammonium cation Hypochlorite anion Monochloramine Water Equation 5
Ifthis reaction is not controlled, the formation ofdichloramine, and trichloramine occurs. 

### NH2

### Cl 

### + HOCl ----+ 

### NHCI2 

### + H 2

### 0 Equation 6 Monochloramine Hypochlorous acid Dichloramine Water

Page 11 of23Dichloramine Hypochlorous acid Trichloramine Water Equation 7
The controlled conditions ofthe systemused for the registered uses (pH> 8, constant temperature, and molar ratios ofammonium ions and hypochlorite) will not likelyproduce dichloramine ortrichloramine.

Environmental Fate and Transport of Ammonium Sulfate Reaction Products Inthe feeder/delivery system under controlled conditions, monochloramine will bethe primary reaction product. Thus the environmental fate ofthese moieties are central to this case. The conventional environmental fate test guidelines are not applicable for monochloramine because it is an inorganic substance. Monochloramine will oxidize and form intermediates. Unlike reactions with organics, typically inorganic reactions are much faster, and therefore not easyto keep tract ofthe intermediates. The intermediates cannotbe classified as degradates in the classical sense. Ammonium sulfate is an inorganic substance, highly water soluble and has no measureable vapor pressure; because ofits ionic nature, octanol/water coefficient cannotbe measured. It is not likely to bioaccumulate in aquatic organisms

. Inliterature some studies report bioaccumulation ofammonia in fish. In clayparticles ofsoils, ammonium ions are adsorbed to the negative adsorption sites. A pHprofile ofammonium (or ammonia) percentages at various pHs are known and are shown inTable 6. Ammonium ions are presentnaturally in various environmental media like water and soils. There is 1-5 ppb ofammoniapresent in the air and the estimatedhalf-life is a few days. Because the central atom is nitrogen, ammonium ions are part ofthe nitrogen cycle (nitrogen fixation) and so it does not stay as ammonia, or ammonium, but goes through many oxidation and reduction steps forming different oxidized and reduced moieties along the way and recycled into the environment. Under aerobic aquatic conditions, ammonium ions are converted through nitrification process. No additional environmental fate data are required for ammonia or ammonium sulfate. Sulfate ions, in this case act as 'spectator ions': do notparticipate in chemical reactions. It is a powerful reducing agent, butneeds strong reducing conditions to initiate chemical reactions. Itis found in environmental media like soils and natural waters. Sulfate ions are likely to mineralize in soils over a period oftime. Monochloroamine: Environmental Fate and Transport For monochloramine the Agency must take into account the physicochemical properties (Table 4), and environmental fate parameters. The environmental fate parameters of monochloramine, sourced primarily from EPI Suite (version 4.0, run September4, 2012), a screening level environmental fate assessment, are summarized as follows:

Page 12 of23• Monochloramine is highly soluble in water and its vapor pressure and Henry's Law Constant are both low (1.16 x10-9mm Hg, and 8.85 xl0- 17 atm-m3/mole respectively). Therefore, it is not expected to volatilize from water surfaces quickly.
• Low

### Kow (-1.19, estimated) therefore it is not expected to bioaccumulate.
• Its Koc (13.2, estimated) 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. (based onHealth Canada study, 1998), depending upon temperature, pH, and salinity. This study and other Canadian studies for aqueous medium decay of chloramines show that in deionized water and seawater mixtures the halflife varied from 0.68 days to 0.98 days.
• Another Canadian study onthe sediment ofGrand River, inNorth Saskatchewan River and Downes Creek showed the halflife of 1.4, 2.5 and 0.05 days. No concrete studies are known that provides data on the dissipation rate of chloramines from soil surfaces.
• Monochloraminehas 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 (version 4.0) models estimate that monochloramine is quicklybiodegraded and it canbe classified as readilybiodegradable. EPI Suite estimates thebiodegradabilityto be 'very fast', which translates into minutes to days. Seebelow for the experimental results from a hydrolysis study.
• PMRA in its most recent Proposed Registration Decision (March 2012)3 on Ammoniumbromide (Fuzzicide) has shown that monochloramine (referred to as bromide activated chloramine(BAC)) hydrolyses in water quickly and at pH 5, its halflife is 15.9 minutes, while at pH 9, the halflife was measured at 184hours (12 days).
• Pulp and paper use ofammonia and ammonium sulfate (and monochloramine) as the active is used in a closed system. Keeping in view the physical/chemical characteristics ofmonochloramine (short hydrolytic halflife, readily biodegradable etc.), the high organic content ofwaste water, and holding time of wastes priorto any discharge to surface water, no detectable levels ofresidual monochloramine are expected in effluent priorto discharge to surface waters. • For once through industrial water systems there maybe circumstances where residual monochloraminehas notbeenreacted priorto discharge depending on the pH ofthe system and receiving waters, and organic content ofwater system. Field dissipation or monitoring data would provide a more refined exposure assessment for these uses.

3Pmra.publications @hc-sc.gc.ca Page 13 of23Dechlorination ofMonochloramine Forthe product registered for use in once-through industrial water systems otherthan pulp and papermills before discharge to the wastewater streams residual monochloramine is measured and, ifdetected, treated with sodium metabisulfite (Na2S2 0 5), which immediately dissociates into sulfite ions (S03

-2 ) which in tumreacts with monochloramine (NH2 Cl) as follows 

## so3-z 

### + Sulfite ion Monochloramine Water Equation 8 Sulfate ion Chloride ion Ammonium ion 

## cr +

The amounts ofthese species produced are nothuge, and the reaction ofreformation of chloramine is not likely. In addition, the amount ofsulfate formed underthese conditions is not large enough to cause dissolved oxygen depletion ofthe waste water streams. Chloramine and Drinking Water Since monochloramine is used as a secondary disinfectant in wastewatertreatments, it is likely to befound in surface and drinking water as a contaminant. Regardless ofsource, EPA has set a maximum drinking water limitfor all contaminants. For chloramines the maximum contaminant limit goal (MCLG) is 4.0 ppm for chloramines in surface waters and 4.00 ppm maximumresidual disinfectant level (MRDL). The water utilities are required to keep the chloramines at4.0 ppm level. Excessive amount ofchloramines, ifpresent in water, canbe easily boiled off. Water Quality Ammonium Sulfate is not identified as a cause ofimpairmentfor any waterbodies listed as impaired under section 303(d) ofthe CleanWaterAct, based on information provided at the Agency's National Pesticides Cause ofImpairment ofWaters website (searched September 6, 2012)4

. In addition, noTotal MaximumDaily Loads (TMDL) havebeen developed ammonium sulfate, based on information rrovided at the Agency's National Pesticide TMDL web site (searched September 6, 2012)

. However, ammonia was identified as a cause ofimpairmentfor 584 waterbodies (unionized (167), total ammonia (158), ammonia (66), and ammonianitrogen (3)) under section 303(d) ofthe CleanWater Act. No Total MaximumDaily Loads (TMDL) have been developed for ammonia, based on informationprovided at the Agency's National Pesticide TMDLweb site (searched September 6, 2012)6

. More information onimpaired waterbodies and TMDLs canbefound at http://www.epa.gov/owow/tmdll

. TheAgency invites submission ofwater quality data for this

4 •http://iaspub.epa.gov/tmdl waters 10/attains nation cy.cause detail 303d?p cause group id=885 5 http://iaspub.epa.gov/tmdl waterslO/attains nation.tmdl pollutant detail?p pollutant group id=885&p pollutant roup name=PESTICIDES http://iaspub.epa.gov/tmdl waterslO/attains nation.tmdl pollutant detail?p pollutant group id=885&p pollutant group name=PESTICIDES Page 14 of23pesticide. To the extent possible, data should conform to the quality standards in Appendix A of the OPP Standard Operating Procedure: Inclusion of Impaired WaterBody and Other Water Quality Data in OPP'sRegistrationReviewRiskAssessmentandManagement Process (see: http://www.epa.gov/oppfead1/cb/ppdc/2006/november06/session1-sop.pdf), in order to ensure they canbeused quantitatively or qualitatively in pesticide risk assessments.



### C. Ecological Effects Summary The major oxidant, monochloramine, formed inthe registered application method of ammonia and ammonium sulfate would be measured as chlorine residual. TheAmbient Water Quality Criteriafor Chlorine

- 1984 document contains a review ofpublic literature on effects ofchlorine and based on the data derives freshwater and saltwater organism acute and chronic water quality criteria as total chlorineresidual (TRC) for freshwater and total residual oxidant (TRO) for seawater. Current ambient water quality criteria for chlorine or total chlorineresidual 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 Jlg/L; • Freshwater Criterion Continuous Concentration= 11 J.tg/L; • Saltwater Criterion Maximum Concentration= 13 Jlg/L; and • Saltwater Criterion Continuous Concentration= 7.5 Jlg/L A review oftoxicity effects data for ammonia, ammonium sulfate, and monochloramine is summarized inthe following sections.



### a. Toxicity to Terrestrial Organisms Two studies conducted using formulated products are available to indicate the toxicity of ammonium sulfate to birds. Both products are practicallynontoxic to birds on an acute oral basis (Table 7). Data are not available for the TGAI (the required test material for this guideline), but the tests with the two formulated products indicate that the TGAI would be only moderately toxic at most. No additional data are needed for the current uses. Mammalian toxicity data are notrequired, and data generated for the humanhealth assessment are available in the human health scoping document.

Page 15 of23Table 7. Summary ofthe Endpoints from Submitted Terrestrial Ecotoxicity Studies for Ammonium Sulfate Study Type Species Test material Toxicity Toxicity MRID& Classification Status 464405-01 Busan 1215 LD50: >2250 TGAI is not Acceptable (7.59% total mglk:g-bw/day more than for Acute- Northern ammonia*) [> 171 mg ailkg bw] moderately toxic formulated Bobwhite product Avian Oral (Colinus 483408-09

850.2100 virginianus) Nalco 60620 LDso: >2003 TGAI is not Acceptable (19.5% ai) mglk:g-bw/day more than for [>390 mg ai!kg bw] moderately toxic formulated product *7.59% total ammoma ts declared as acttve mgredtent onthe label under the Active Ingredtent statement, and the term "TotalAmmonia" refers to the sum ofun-ionized ammonia and ionized ammonia (NH3(aq)**+~"")expressed** as the equivalent ionized ammonia content. b. Toxicity to Aquatic Animals There are National Ambient Water Quality Criteria (AWQC) for Ammonia (EPA 1989, 1999, 2009). Ammonium sulfate is one ofseveral ammonium salts (ammonium chloride; phosphoric acid, diammonium salt; ammoniumbicarbonate; nitric acid ammonium salt; ammoniumphosphate) in addition to testing with ammoniaused to develop the water quality criteria. From these data, depending onthe environmental pH and temperature conditions, ammonia toxicity canrange from slightly toxic to highly toxic to aquatic organisms. The toxicity ofammonia is dependent onpH, and temperature; toxicity is also dependent on ionic strength but infresh water this is minor compared to pH and temperature. Therefore water quality criteria values for ammonia are written in terms ofpH and temperature for freshwater systems. The current freshwater AWQC for ammonia are expressed in terms oftotal ammonia nitrogen (TAN), concentration ofNH3 plus**N~**+ expressed as nitrogen (N) concentration (note this differs from how the labels express total ammonia). The saltwater AWQC are expressed as total ammonia (TA), concentration ofNH3 plus**N~** expressed as total NH3 concentration. The following freshwater AWQC provided are the current criteriafrom the EPA 1999 AWQC document. When this risk assessment is performed, any updated ammonia criteria will beused in the assessment. Freshwater • Acute Criterion (Criterion MaximumConcentration (CMC) as mg TANIL): Wh 1 

### CMC 0.275 39.0 o ere sa mon are present 

### = 1+107.204-pH 

### + 1+ 1 opH-7.2o4
o Where salmon are absent 

### CMC 

### = 0" 411 

## + 58" 4 1+107.204-pH 1+10PH-7.204

Page 16 of23• Chronic Criterion (Criterion Continuous Concentration (CCC)) as mg TANIL:
o Where fish early life stages are present

_ 0.057 2.487 ( 0.028X(25-T)) CCC

- 1 

## + 107.688-pH 

## + 1 

## + 10PH-7.688 X

### MIN 2.85, 1.45 X 10
o Where fish early life stages are absent CCC = 0.057 

### + 2.487 X 1.45 X 100

.028x(25-MAX(T,7)) 1 

## + 107.688-pH 1 

## + 10PH-7.688 where temperature, T, is in degrees Celsius. 

### Table 8. Examples ofacute and chronic ammonia A WQC for freshwater, expressed as total ammonia nitrogen CMC,m2NIL1 CCC,m2NIL1 pH Salmonids Salmonids Fish early life stages present Fish early life stages absent Present Absent 14 °C 22°C 30°C lS°C >lS°C 

### 6.5 32.6 48.8 6.67 4.12 2.46 6.46 Same as fish 

### 7.0 24.1 36.1 5.91 3.65 2.18 6.11 7.5 13.3 19.9 4.36 2.69 1.61 4.51 early life 

### 8.0 5.62 8.40 2.43 1.50 0.897 2.52 stage 

### 8.5 2.14 3.20 1.09 0.672 0.401 1.13 present

I• - + Total ammoma mtrogen -concentratiOn ofNH3 plus concentration of**N~** expressed as mtrogen (N). 

### Saltwater The acute CCC and the chronic CMC for un-ionized ammonia (NH3) is 0.233 mg/L and 0.035 mg/L, respectively. These criterion concentrations based ontotal ammonia are provided in Tables 1 and 2 ofEPA's saltwater AWQC for ammonia document (1989); excerpts from these tables are provided for the acute CMC inTable 9 and the chronic CCC in Table 10. 

### Table 9. Excerptfrom EPA 1989 ofacute CMC saltwater A WQCfor ammonia expressed as total ammonia1 Salinity

pH 10Wk2 20Wk2 30Wk2 Temperature Temperature Temperature S°C lS°C 2S°C S°C lS°C 2S°C S°C lS°C 2S°C 

### 7.0 191 92 44 200 96 44 208 102 48 7.6 48 23 11 50 23 11 54 25 12 8.0 19 9.4 4.6 20 9.8 4.8 21 10 5.0 8.4 7.9 3.7 1.3 8.1 4.0 2.0 8.7 4.2 2.1 9.0 2,1 1.1 0.67 2.3 1.2 0.69 2.3 1.2 0.71 I• - + Total ammoma mtrogen- concentration ofNH3 plus concentration**ofN~** expressed as un-tomzed ammoma (NH3).

Page 17 of23

### Table 10. Excerptfrom EPA 1989 ofchronic CCC saltwater A WQC for ammonia expressed as total ammonia1 Salinity

pH 10 g/kg 20 g/kg 30 g/kg Tem_l)_erature Temperature Temperature S°C lS°C 2S°C S°C lS°C 2S°C 5°C lS°C 2S°C 7.0 29 14 6.6 30 14 6.6 31 15 7.2 7.6 7.2 3.4 1.7 7.5 3.4 1.7 8.1 3.7 1.8 8.0 2.9 1.40 0.69 3.0 1.5 0.72 3.1 1.6 0.75 8.4 1.2 0.56 0.29 1.2 0.59 0.30 1.3 0

.62 0.31 9.0 0.31 0.17 0.10 0.34 0.18 0.10 0.34 0.19 0.08 + Total ammoma mtrogen = concentratiOn ofNH3 plus concentration of**N~** expressed as un-10mzed ammoma (NHJ). Table 11 provides a summary ofammonium sulfate specific data submitted byregistrants and literature values reported inthe 2009 draft freshwater AWQC for ammonia and the 1989 saltwaterAWQC for ammonia. However, this is a relatively small data set as compared to the more expansive andbridgeable ammoniatoxicity data setused for setting ammonia criteria. Ammonium sulfate is one ofseveral ammonium salts (ammonium chloride; phosphoric acid, diammonium salt; ammonium bicarbonate; nitric acid ammonium salt; ammoniumphosphate) in addition to ammonia used to develop ammonia criteria. No additional ammonium sulfate or ammonia data are required for registration review. However, the Agency expects thatunderuse application methods, exposure ofaquatic organisms will notbeto ammoniabutrather to the monochloramine generated from combining the end-use products with sodiumhypochlorite as specified onthe product labels. Other data are available to categorize the toxicity ofchloramines to aquatic animals. These data, generated for ammoniumbromide mixed with sodiumhypochlorite, categorize chloramines as being acutely highly to very highlytoxic to freshwater and estuarine/marine animals (Table 12). To support the treatment ofonce-through industrial water system uses, acute toxicity data for monochloramine are needed for estuarine/marine fish and invertebrates and chronic data are needed for both freshwater and estuarine marine organisms. 

### Table 11. SummaryoftheEndpoints from Fish and Aquatic InvertebrateEcotoxicity Studiesfor Ammonium Sulfate. Study Type Species Test Exposure method, Toxicity1 Toxicity MRID& material pH, Temperature Classification Status Busan 1215

(7.59% 96-hrLC50: >126 mg Practically 464351-06

total ailL nontoxic Acceptable Acute- Rainbow trout ammonia2) Nalco Freshwater (Oncorhynchus 60620 96-hr LC50: >140 mg Practically 483512-01 Fish mykiss) (19.5% ai) ailL nontoxic Acceptable Ammonium 96-hr LC5o: 51.06 mg Qureshi et al. sulfate S, 7.95, 15 °C NIL Slightly toxic 1982 cited in (46.46 mg NIL atpH=8) EPA2009

Page 18 of23Exposure method, Toxicity MRID& Test Toxicity 1 Classification Status Study Type Species material pH, Temperature Thurston and 96-hrLC50: 36.73 mg Slightly toxic Russo 1983 Ammonium F, 7.9, 12.4 °C NIL cited inEPA sulfate (29.91 mg NIL atpH=8) 2009 Thurston and 96-hrLC50: 39.25 mg Slightly toxic Russo 1983 Ammonium F, 7.94, 12.5 °C NIL cited inEPA sulfate (35.06 mg NIL atpH=8) 2009 Busan 1215 96-hrLC50: >117 mg Practically 464351-05 Bluegill (7.59% ailL nontoxic Acceptable total sunfish ammonii) (Lepomis Nalco 96-hrLCso: 62 Slightly toxic 483408-07 macrochirus) 60620 mg ai/L Acceptable (19.5% ai) Rice and Pink salmon 96-hrLC50: 230.5 mg Slightly toxic Bailey 1980 (Oncorhynchus Ammonium S, 6.4, 4.3 °C NIL cited in EPA

gorbuscha), sulfate (38.33 mg NIL at pH=8) 2009 late alevins Pink salmon 96-hrLC50: 277.7 mg Slightly toxic (Oncorhynchus Ammonium S, 6.4, 4.3 

### oc NIL

gorbuscha), sulfate (46.18 mg NIL at pH=8) late alevins Knoph 1992

Atlantic Ammonium 16 Tests 20.45 to 69.49 mg NIL Slightly toxic cited in EPA salmon (Salmo sulfate S, 6.0 to 6.45, 1.8 atpH=8 2009 salar) to 17.1 °C Pacific tree Schuytema 96-hr LC50: 103.1 mg and Nebeker frog Ammonium R, 6.7, 22 °C NIL Slightly toxic 1999a cited (Pseudacris sulfate (19.45 mg NIL at pH=8) inEPA 2009

regilla), Embryo Pacific tree Schuytema frog 96-hrLC5o : 116.4 mg Slightly toxic and Nebeker (Pseudacris Ammonium R, 7.3, 22 °C NIL 1999a cited

regilla), sulfate (37.3 mg NIL at pH=8) in EPA 2009 Gosner stage 26-27 Schuytema Acute- Clawed toad 96-hrLC50: 33.2 mg Moderately and Nebeker Amphibian (Xenopus Ammonium R, 7.2, 22 °C NIL toxic 1999acited laevis), sulfate (9.524 mg NIL at pH=8) in EPA 2009 embrvo Schuytema Clawed toad 96-hr LC50: 60.71 mg Slightly toxic and Nebeker

(Xenopus Ammonium R, 7.2, 24

### oc NIL 1999 cited in

laevis), sulfate (17.27 mg NIL at pH=8) EPA2009 embryo Schuytema Clawed toad 96-hr LC50: 135

.9 mg Slightly toxic and Nebeker

(Xenopus Ammonium R, 7.15, 22 °C NIL 1999b cited laevis), Gosner sulfate (36.59 mg NIL at pH=8) inEPA2009

stage 26-27 Acute- Water flea Busan 1215 48-hrEC50: >120 mg Practically 464351-07 Freshwater (Daphnia (7.59% ailL nontoxic Acceptable Invertebrate total

850.1010 magna) ammonia2)


### Page 19 of23Study Type Species Test Exposure method, Toxicity' Toxicity MRID& material pH, Temperature Classification Status

Nalco 48-hrEC50: >789 mg Practically 483408-06 60620 (19.5% ai) ailL nontoxic Acceptable Acute- Water flea 48-hr EC50: 48.5 mg Manning et Freshwater Ammonium NIL Invertebrate (Ceriodaphnia sulfate R, 7.4, 23 °C (15.06 mg NIL at pH =8 Slightly toxic al. 1996 cited dubia) and 25 °C) in EPA 2009 Acute- Red drum S, 8.0-8.2, 25-26 Holt and Estuarine/ (Sciaenops Ammonium °C, 28-30 parts 96-hr LC50: 0.545 mg Highly toxic Arnold 1981

Marine ocellatus), sulfate per thousand NH31L cited in EPA

Fish embryo-larva salinity 1989 Exposure method: S = static, R = static renewal, F = flow-through 1Acute values in the freshwater, ammonia ambient water quality criteria document are expressed as total ammonia nitrogen (mg NIL) and because ammonia toxicity is related to pH and temperature are normalized to pH 8 and temperature 25°C as per equations provided in the 1999 criterion document for comparison. 2 7.59% total ammonia is declared as active ingredient onthe label under the Active Ingredient statement, and the term "TotalAmmonia"refers to the sum ofun-ionized ammonia and ionized ammonia (NH3(aq)**+~+)expressed** as ionized**~**+. Table 12. Summary ofEndpoints from Submitted Fish and Aquatic Invertebrate Ecotoxicity Studies for Ammonia Bromide mixed with Hypochlorite to FormMonochloroamine. Study Type Species Test material Toxicity Value Toxicity MRID& Classification Status Rainbow trout Ammonium Very highly 447213-13 (Oncorhynchus bromide 96-hrLC50: 58**~g** Clz/L Acute- my kiss) (99.9% ai) toxic Acceptable FreshwaterFish Bluegill in 10% 850.1075 sunfish hypochlorite 96-hrLCso: 290**~g** Clz/L Highly toxic 447213-12 (Lepomis solution with Acceptable macrochirus) carbonate Acute- Sheepshead buffer Estuarine/marin minnow 96-hrLC50: 360**~g** Clz/L Highly toxic 447213-16 eFish (Cyprinodon Acceptable 850.1075 variegatus)AcuteFreshwater Waterflea 48-hrEC50: 23**~g** Clz/L Very highly 447213-14 Invertebrate toxic Acceptable 850.1010AcuteEstuarine/ Mysid Very highly 447213-15 marine (Mysidopsis 96-h LC50: 36**~g** Clz/L Invertebrate bahia) toxic Acceptable 850.1035 Acute- Eastern oyster Estuarine/marin Very highly 447213-17 e Invertebrate (Crassostrea 96-h ECso: 18**~g** Ch/L toxic Acceptable 850.1025 virginica)

Page 20 of23

### c. Toxicity to Aquatic Plants No aquatic plant toxicity datahavebeen submitted for ammonia or ammonium sulfate. However, there is ammonia toxicity data with aquatic plants that has been reviewed for AWQC development (EPA 1989, 1999, 2009)

. While nitrogen is an important nutrient for plants, excess ammonia canbe toxic to both freshwater and saltwaterplants. No additional data is required for ammonia for this registration review assessment. Two studies are available to assess the effects ofchloramines on duckweed and green algae

. These studies indicate that chloramines adversely affect aquatic plants at low concentrations (Table 13). These data canbeused to support ammonium sulfate as well. Data for monochloramine is also needed for a marine diatom, freshwater diatom, and blue-green algae to supportthe once-through industrial water system uses. 

### Table 13. Summary ofthe Endpoints from Submitted Aquatic Plant Ecotoxicity Studies from Monochloramine. Study Type Species Test material Toxicity Value Toxicity MRID& Classification Status Aquatic Plants- Duckweed Ammonium 7-day EC50: 670 11g n/a 452052-02 Vascular (Lemna gibba) bromide Ch!L Acceptable 850.4400 (99

.9% ai) Aquatic Green algae in 3% hypochlorite Plants- solution with 72-hECso: 28 Jlg 452052-01 Nonvascular (Pseudokirchneriella carbonate buffer Ch/L n/a Acceptable

850.5400 subcapitata)



### Environmental Fate and Ecological Effects Data Gaps and Anticipated Work The Agency anticipates performing a refined risk assessment on the once-through industrial water systemuses ofammonia and ammonium sulfate. To perform this assessment a field dissipation study is needed and additional monochloramine effects data with aquatic organisms are needed. No further risk assessment for the pulp and paperuse ofammonia and ammonium sulfate is anticipated at this time. 

### Environmental Fate Data Gaps There are no environmental fate data gaps for ammonia, ammonium sulfate orreaction product, monochloramine for the pulp and paper use scenario. However, to allow a refined risk assessment for use with once-through industrial water systems the following fate data is required to address the fate ofmonochloramine: 835.6200: Aquatic Field Dissipation Study.

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### Ecological Effects DataGaps The following ecotoxicity guideline studies are needed with monochloramine to support the once-through industrial water system uses ofammonia and ammonium sulfate: 850.1400

850.1300 850.1350 850.4100 850.4500 850.4550 Fish early-life stage: 1 freshwater species and 1 estuarine/marine species Aquatic invertebrate life-cycle: 1 freshwater species and 1 estuarine/marine species Seedling emergence, Tier II

- dose response, rice Aquatic plant growth (algal) Tier II (dose response): marine diatom, freshwater diatom, cyanobacteria (blue-green algae) 

### Endangered Species Determination The Agency has determined that the use ofammonia and ammonia sulfate in oncethrough cooling towers has a potential to expose aquatic organisms to monochloramine. Because monochloramine is highly toxic, listed freshwater and estuarine/marine organisms maybe at risk. An ecological risk assessmentplanned during registration review will allow the Agency to determine whether an antimicrobial pesticide's use has "no effect" or "may affect" federally listed threatened or endangered species (listed species) ortheir 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.



### REFERENCES Holt, G.J. and C.R. Arnold. 1983. Effects ofammonia and nitrite on growth and survival ofred drum eggs and larvae. Trans. Am. Fish. Soc. 112:314-318. Knoph, M.B. 1992. Acute toxicity ofammoniato Atlantic salmon (Salmo salar) parr. Camp. Biochem. Physiol. Camp. Pharmacal. Toxicol. 10(2): 275-282. Manning, T.M., S.P. Wilson and J.C. Chapman. 1996. Toxicity ofchlorine and other chlorinated compounds to some Australian aquatic organisms. Bull. Environ. Contam. Toxicol. 56(6): 971-976. Qureshi, A.A., K.W. Flood, S.R. Thompson, S.M. Janhurst, C.S. Inniss and D.A. Rokosh. 1982. Comparison ofa luminescentbacterial test with otherbioassays for determining toxicity ofpure compounds and complex effluents. In: Aquatic toxicology and hazard assessment, 5th conference. Pearson, J.G., R.B. Foster and W.E. Bishop (Eds.). ASTM STP 766. American Society for Testing and Materials, Philadelphia, PA. pp. 179-195.

Page 22 of23Rice, S.D. and J.E. Bailey. 1980. Survival, size and emergence ofpink salmon, Oncorhynchus gorbuscha, alevins after short and long-term exposures to ammonia. Fish. Bull. 78(3): 641-648. Schuytema, G.S. and A.V. Nebeker. 1999a. Comparative effects ofammonium and nitrate compounds on Pacific treefrog and African clawed frog embryos. Arch. Envion. Contam. Toxicol. 36: 200-206. Schuytema, G.S. and A.V. Nebeker. 1999b. Comparative toxicity ofammonium and nitrate compounds to Pacific treefrog and African clawed frog tadpoles. Environ. Toxicol. Chern. 18(10): 2251-2257. Thurston, R.V. and R.C. Russo. 1983. Acute toxicity ofammonia to rainbow trout. Trans. Am. Fish. Soc. 112: 696-704. United States Environmental ProtectionAgency (EPA). 1989. Ambient Water Quality Criteria for Ammonia (Saltwater)- 1989. Office ofWater, Regulations and Standars Criteria and Standards Division, Washington, DC. EPA440/5-88-004. United States Environmental Protection Agency (EPA). 1999. 1999 Update ofAmbient Water Quality Criteria for Ammonia. Office ofWater, Washington, DC. EPA-822-R-99-014. United States Environmental Protection Agency (EPA). 2008. Ecological Hazard and Environmental Risk Assessment ofAqueous Ammonia (Busan 1215) For the Proposed Use in Industrial Water Systems. Risk Assessment and Science Support Branch, Antimicrobials Division, March 20, 2008. United States Environmental ProtectionAgency (EPA). 2009. Draft 2009 Update. Aquatic Life Aquatic Life Ambient Water Quality Criteria for Ammonia- Freshwater. Office of Water, Washington, DC. EPA-822-D-09-001. United States Environmental Protection Agency (EPA). 2011. Ecological Risk Assessment for Nalco 60620 which is an end-use product containing ammonium sulfate. The proposed registration ofthis product is for use in controlling microorganisms using an in-situ generating system for use inpulp and paper mills. Risk Assessment and Science Support Branch, Antimicrobials Division, April 28, 2011.

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