# E' ph-#4 .-Q)cpr_:~,oDs . .rs 63 UREA, REACTION PRODUCTS WITH FORMALDEHYDE



## Submission For Fulfilment of Data Requirements for Urea, Reaction Products with Formaldehyde

Under TSCA Section 4 1 . Chemical Name: Urea, reaction products with formaldehyde 2 . CAS Number : 68611-64-3 3 . Industry Sponsor : The Fertilizer Institute WilliamHerz 

### 820 First Street NE, Union Ctr Plaza Ste 430 Washington, DC20002 Tel : (202) 515-2706 I 9 . Date of Submission: July 2007; Revised March 2008 10. Comments: Urea, reaction products with formaldehyde is not manufactured or processed for distribution in commerce as chemical substance per se and, relative to the fertilizer industry, has no commercial purpose separate fromthesubstance mixture or article ofwhich it may be a part (40 CFR § 710 .4(d)) . Urea, reaction products with formaldehyde (UF) is primarily methylene diurea (MDU, CAS No 13547-17-6) and relies on data presented for Urea (CAS 57-13-6; Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme (1994

; seeattached documents) . Both UF, including MDUand Urea are enzymatically hydrolyzed to ammonia and carbon dioxide in theenvironment and in mammalian systems . Isopropyl methvlenediurea (CAS No. 6104-30-9 ; chemical name 1,1'-(2-methvluropane-1,1-divl)diurea) is considered to be an analog of MDU

. The only difference between themis the substitution of isopropyl for H on the meth

ylene carbon. 

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# CONTAINS NOCBI

### UREA, REACTIONPRODUCTSWITH FORMALDEHYDE 

## CONTENTS 1 IDENTITY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . 5 1 .1 Identification ofthe Substance . . . . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 5 1 .2 Physico-Chemicalproperties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . .I- 2 GENERAL INFORMATION ON EXPOSURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 2.1 Environmental Exposure and Fate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 7 2.1 .1 Sources of Environmental Exposure . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 2 .1 .2 Photodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 7 2 .1 .3 StabilityinWater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . , . 2.1 .4 Stability in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . .~- 2 .1 .5 Transport between Environmental Compartments. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .~ 2 .1 .6 Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . .. . . . . . . .8 3 HUMAN HEALTH HAZARDS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . .-9 3.1 Effects on Human Health . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 9,

- 3.1 .1 Toxicokinetics, Metabolism and Distribution. .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 .2 Acute Toxicity.. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~

_ . 3.1 .3 Repeated Dose Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.1 .4 Mutagenicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . 1~1 3.1 .5 Toxicity for Reproduction. . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. ..I), 4 HAZARDS TOTHE ENVIRONMENT . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . ~ 4 .1 Aquatic Effects. . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . " 5 RECOMMENDATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12 6 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . .13 

# - F 

# - Deleted. 6

- Dele,betl :7 Deleted : 7 Deleted : 7 "l Deleted

: 8 Deleted : 8 Deleted : 8 Deleted . 8 Deleted : to Deleted : 11

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### UREA, REACTIONPRODUCTSWITH FORMALDEHYDE 

## Tables Table 1 Summary of physico-chemical properties: MDU. . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . .6 Table 2 Summary of acute toxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Table 3 Summary of repeated dose toxicity . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . " . .. - -. - Delebed: 10

### UREA, REACTION PRODUCTS WITHFORMALDEHYDE 

## Submission for Fulfilment of Data Requirements for Urea, Reaction Products with Formaldehyde

Under TSCA Section 4 1 IDENTITY 1 .1 Identification of the Substance 

### CAS Number: 68611-64-3 Primary component : Methylene diurea (MDU) 13547-17-6 Molecular Formula: Unknown, Variable, Complex, Biological (UVCB) CH4N20

.CH20 W99 

### (MDU = C3H8N4O2) Structural Formula: NH,

NH: Primarycomponent, MDU Molecular Weight: NA (MDU = 132.12) Synonyms: Formaldehyde, urea adduct UF 1 .2 Physico-Chemical properties Urea, Reaction Products with Formaldehyde (UF) is an Unknown, Variable, Complex, Biological substance

. The physical chemical properties ofthis mixture have not been determined. The physical chemical properties ofthe major component of UF are provided.

### UREA, REACTIONPRODUCTS WITHFORMALDEHYDE

Table 1 Summary ofphysico-chemical properties: 1VII)U Property Value Reference Physical state solid Melting point 212-214°C Hays and Haden (1966) Boiling point Not applicable Relative density No data Vapour pressure Not applicable Water solubility 25 g/i Hays and Haden (1966) Partition coefficient noctanoUwater (log value) -3.01 Epiwin, v3.20 2 GENERAL INFORMATIONON EXPOSURE Urea, reaction products with formaldehyde (UF) is not a commercial product for the members of The Fertilizer Institute (TFI) . Typically, during production, 95%of the domestic urea producers, condition urea with a formaldehyde-based additive. In the urea production process, formaldehydebased additives (FBA) are injected into molten urea or a hot urea solution. At process temperatures (- 280°F), formaldehyde reacts to form methylenediurea (MDU, 13547-17-6) and water. MDU is used as a conditioning agent, which reduces solids caking during storage and urea dust formation during transport and handling (TFI, 2007) . The final product (fertilizer) contains unreacted urea, methylenediurea, methylenetriurea and longer chain polymers. Free formaldehyde is generally not present in UF Table 2

) . Recent analysis of urea fertilizers indicate that of theca 19. 8 million short tons of urea fertilizer produced and imported in the US nearly 99 percent (ca 19 . 6 million short tons) has been shown to contain 0-0 .5 npm free formaldehyde. Only solid urea fertilizer has been shown to contain free formaldehyde, at a range of 0-18. 7 pam MDU is the principle compound formed when the formaldehyde additive reacts with hot urea (USEPA, no date specified; Murray et al ., 1982) . Current levels of MDUin fertilizer grade urea are 1 .3-2.7% . Table 2 Types ofUrea and Free Formaldehyde Levels (Fertilizer Year Endine June 30 2_006)

-Analv ~ Type of Urea US Production Free Formaldehyde, Explanation Fertilizer and import volume, Million short tons Dam

Urea Ammonium 10.1 M Q Urea in liauid form does not have Nitrate (UAN Solutions formaldehyde or FBA added Urea, solid (prill or - 0 .2 M * Variati d granular) 0-18.7 on appears to epend on manufacturingprocess and starting compound Urea, solid (nrill or -V 8 M Va i ti granular) 0-0.5 r a on annears to depend on manufacturing process and starting comnound Technical Grade Urea 1 .45 M o Technical erade urea also does not a!1 o. ., . . EDA . . . _ have FBA added ethod 8315Awith a detection limit of! ppm . - - - Fonnatted Table

Fonnatbed

: Normal, Space Before: 6pt J tFormatl :ed

: Normal, Space Before: 6pt

6

### UREA, REACTION PRODUCTS WITH FORMALDEHYDE

~ ,Some urea fertilizer manufactures r~orted the manufacture and import of biuret and urea reaction_ products associated with the manufacture and import of urea fertilizer in TSCA Inventory Update Rule (IUR) Form U submissions including the 2002 reports for activities in 2001- EPA Form Numbers 6511017 and 65011017. In 2003, TFI petitioned EPAfor a partial reporting exemptionfor fertilizers and certainfertilizer materials including biuret and urea reaction products frominventory update reporting requirements proposed for 2006 and beyond. In November 2003 and December 2004, EPA issued letters to TFI concluding that biuret and urea reaction products with formaldehyde are "impurities" as defined in 40 CFR . § 720 .3 and therefore were notsubject to 2006 IUR reporting

. The applicable provision of the now final regulation is § 710 .50(c) which defines manufacturing a chemical substance "in a manner described in § 720 .30(g) or (h)" ofthe regulations as an activity forwhich reporting is not required. A similar regulation, § 710 .30(c), applies to 2002 IUR reporting . Some of the urea fertilizer manufacturers 2002 IUR reports included chemical substances for which it is now clear, based on EPA's November 2003 and December 2004 interpretation letters, that reporting was not required. These urea fertilizer manufacturers revised and resubmitted 2002 FormUReports removing biuret (CAS No. 108-19-0) and urea reaction products with formaldehyde (CAS No. 68611-64-3) . MDUis the largest component of the methyleneurea polymers found in ureafotmfertilizers and is used as a structural analogue to represent the smaller percentage of larger polymeric methyleneurea polymers as described by CAS No 68611-64-3. In addition, MDU (and other UFs) is degraded in the environment to urea, ammonia and carbon dioxide (Jahns and Kaltswasser, 2000 ; Kaempffe and Lunt, 1967) . For example, MDU degrades ca. 90%in 14 days (Katz and Fassbender, 1966) . Biode~4radation data for 1,1'2-(2-methylpropane-l .l-diyl)diurea (CAS No 6104-30-9), an analog of MDU, are available throuQli the MITI database (2002) . The results indicate the analoa biodegrades 78 - 100%, by indirect and direct analysis. respectively, over -1 weeks. ,Fromthe biodegradation _ pen-,pective, the analog is similar but in theorv might be slower to degrade than MDU_piven its -_, . .- - - --- ---- .. .._ - substitution (of isopropyl for H) on the methvlene carbon. Data were not located regarding the degradation of UF in the mammalian gut; structure activity analysis in combination with information regarding degradation by microorganisms suggests UF will readily degradeto urea (and then to ammonia and carbon dioxide) . Data from urea UNEP Publications, date not specified) are used to provide additional information for UF. As stated in the UNEP document, "urea is an important endogenous product ofmammalian metabolism . Urea appears to cause little or no toxicity to most mammalian species (ruminants are an exception) and humans at reasonable dose levels. Further, the EPA has indicated that urea poses no risk concerns within the limits of the existing tolerance exemptions (_http://www .epa.eov/onnsrrdl/rereQistration/urea/) , urea is approved for several human therapeutic uses (httn://216.239.51 .104/search?q=cache:n1264Z8FFIJ :www

.fda.eov/cder/o¢d/rid/12154s24 .ndf+FDA+cateeorv+C+urea&h1=en&ct=clnk&cd =1&gl--us ) and is considered "Generally Recognized As Safe" (GRAS) as affirmed by the U . S. Food and Drug Administration for use in food (21 C .F.R. § 184.1923 Urea. Title 21 - Food and Drugs) . 2.1 Environmental Exposure and Fate 2.1 .1 Sources of Environmental Exposure 2 .1 .2 Photodegradation The overall OH Rate Constant was = 1 .97 E-12 cm3/molecule-sec with a half-life = 0 .5 days (Epiwin, v3.20, RL=2) . - Delebed: y 

# J

### UREA, REACTION PRODUCTS WITHFORMAI .DEHYDE

2 .1 .3 Stability in Water Hydrolysis studies were not available. Modeling indicates that the hydrolysis rate will be extremely slow(tl/2 > 1 year) (Epiwin, v3.20, RL=2) . 2.1 .4 Stability in Soil The rates of nitrification of methylenediureas were investigated in soil (Hays and Haden, 1966). Urea reached 80%

conversion to nitrate after 12 days, MDUnitrification was slower (about 30% in 12 days; 90%in 14 days) and dimethylene diurea (DDU) nitrification was slower still (about 15% in 12 days; 50%in 14 days) . In a second experiment, water was added to the soil 10 days before the addition ofthe test substances to allow the build-up of nitrifying bacteria. The induction period was nearly eliminated for urea (100%in 8 days), while MDU and DDU required 8 or 9 days to begin production of significant amounts of nitrate (after 16 days about 90%for MDU and about 30%for DDU) . Similar results were reported in which 85%nitrification of MDU and DDUwas observed in three weeks; 68%of trimethylene tetraurea and <5%tetramethylene pentaurea was observed in the same period (Kaempffe and Lunt, 1967; Long andWinsor, 1960) . 2.1 .5 Transport between Environmental Compartments Ureaforms such as MDUand DDU have decreased rates of leaching compared to urea (Hays and Haden, 1966) . About 90% of the applied ureaformwas retained in soil ; about 10%of the applied urea was retained in soil . With the more drastic leaching procedure (procedure 2) the retention of ureafonn nitrogen was reduced to 76%, dueto low solubility. The EQC Level III Fugacity model (Epiwin, v3.20, RL=2) was used to evaluate the fate, transport and distribution of MDU between environmental matrices. Level III fugacity modelling, using loading rates of 1000 kg/h each for air, soil and water, shows the following percent distribution when it is released simultaneously to all three compartments: Air = 4.12E-11% ; Soil = 60

.9; Water = 39% ; Sediment = 0

.713% . 2.1 .6 Biodegradation Nitrogen content was made the limiting factor in the test media in a modified Warburg test in which MDU, Dimethylentriurea, Trimethylenetetraurea, and the low, intermediate, high and total combined molecular weight fractions ofureaformwere tested (Katz and Fassbender, 1966, RL=2) . Increases in chain length decrease biodegradability; MDUwas ca. 80 and 90% degraded in 8and 14 days, respectively. Dimethylenediurea was degraded ca. 70%degradation in 8 and 14 days. Trimethylenetetraurea degraded ca. 40 and 60% in 8 and 14 days, respectively. The lowMW fraction degraded 100%in 11 days; the intermediate MW fraction degraded 70% in 11 or after 14 days, the high MW

fraction degraded <10%in 11 days and ca. 10% after 14 days and the combined MW fractions degraded ca. 66% after 14 days. In garden soil, the microbial degradation of 7.5mM MDU as the sole source of fixed nitrogen was followed at 26C (Jahns and Kaltswasser, 2000, RL=2) . 100%of the MDU was degraded by 4days. Epiwin modeling indicates MDU is likely to be biodegradable (Epiwin, v3.20, RL=2) . In a modified MITI test (OECD 301C), 1,1'2-(2- methylpropane-l,l-diyl)diurea (CAS No 6104-30-9), an analog of MDU, biodegradation rates of 78% and 90%to 100°/o were achieved by indirect (BOD: NH3) and direct analysis (TOC and HPLC), resaectively, over 4 weeks. Fromthe biodeeradation perspective, the analog is similar but in theorv might be slower to degrade than MDU given its substitution (of isopropyl for H) on the methyl _ene_carbon.

### UREA, REACTION PRODUCTS WITH FORMALDEHYDE

Urea is ultimately biodegradable in inherent biodegradability test (OECD TG 302 B) . In semicontinuous activated sludge (SCAS) urea is biodegraded on the average of 93-98% in 24-hour cycle . The main mode ofdegradation is enzymatic mineralization. In soil andwater urea is expected to biodegrade fairly rapidly to ammonia and bicarbonate if temperature is not too low . Ammonia is a volatile gas in alkaline solutions. In natural waters, most ammonia appears in the form of ammonium, fromwhich nitrogen is oxidized IRPTCData Profile Identifiers, Physical and Chemical properties 3 as the result of bacterial action, forming nitrite and nitrate. According to US-EPA PCGEMS-model hydrolysis of urea is expected to be extremely slow(TI/2 > I years) (UNEP, date and RL not specified) . 

### 3 HUMAN HEALTH HAZARDS Data from urea (UNEP Publications, date not specified) are used to provide human health hazard information for UF. 3.1 Effects on Human Health 3.1 .1 Toxicokinetics, Metabolism and Distribution Data were not located regarding the degradation of UF in the mammalian gut; structure activity analysis in combination with information regarding degradation by microorganisms suggests UF degrades to urea (and then to ammonia and carbon dioxide) . These hydrolysis products can then be used to synthesize amino acids. The complete hydrolysis and deamination of protein involves numerous enzymes. Urea is extremely soluble in water and oral doses are rapidly absorbed and distributed in humans. Urea is a normal human body constituent and is constantly being produced through amino acid and protein metabolismwhere urea is formed through acyclic mechanism . 3 .1 .2 Acute Toxicity The acute toxicity of UF has not been studied . The acute toxicity by urea is well delineated by the oral route . Toxicity is lowin mammals other than ruminants, especially cattle, and sheep, in which the rumen micro-organisms contain urease activity and metabolize urea to ammonia at a high rate. In mice and rats, urea is oflow toxicity even by the subcutaneous and intravenous route (UNEP, date and RL not specified) . Examples of specific toxicity values published for urea are provided for comparison in Table 2. Table 2 Summary of acute toxicity: Urea Species Value (mg/kg bw) RUReference Urea Sheep Oral LD50 = 510 Not specified/FDA, 1978 Rat Oral LD50 =14300 (M) ; = 15000 (F) Not specified/Sato et al ., 1978 3 .1 .3 Repeated Dose Toxicity Repeated dose toxicity studies with UF have not been conducted.

### UREA, REACTIONPRODUCTS WITH FORMALDEHYDE

Repeated dose studies were located for urea which was not presented in the UNEP document. Five groups of steers were fed a high-roughage, low-concentrate wintering ration in dry lot for 84 days (Berry et al ., 1956; RL=2) . The basal ration was made up of 36 .5%Atlas silage (hay basis), 24% cottonseed hulls, 6%alfalfa leaf meal, 11% blackstrap molasses, and from 13% to 20% milo grain and 1%minerals (bonemeal and salt) . The crude protein supplements used were 7.5%cottonseed meal (Group 1), 1%feed-urea (Group 2), 1%crude biuret (Group 3), 1 .5% a mixtureofcrude biuret and feed-urea (Group 4), and 1 .25%of a urea-fatty acid complex (Group 5) . The total intake of each group was adjusted to that of the lowest consuming group . This was accomplished by hand feeding . Each ration was calculated to supply equal amounts of dry matter, total digestible nutrients, and except for Group 4, protein equivalent. Group 4 was 1 .4%higher in crude protein equivalent. The urea-fatty acid complex was 75% urea and 25%cottonseed foots. Animals were observed for signs of toxicity and average weight gain was calculated at study termination. The average gains made by the control group and the urea group (Group 2) were not significantly different. However, when the urea was replaced with the crude biuret (Group 3), a significantly lower gain resulted. This group also consumed the least feed and therefore, restricted the intake of the other groups. When additional urea was included with the crude biuret (Group 4), the average gain was statistically significantly . Thus, simply adding urea overcame the adverse effects of biuret. Although Group 4 gained slightly more than the group fed urea alone (Group 2), the difference was not significant . The increase in daily gain may suggest that contrary to the results obtained with Group 3, the biuret nitrogen was utilized to some extent by the rumen bacteria. The group fed urea-fatty acid complex (Group 5) gained essentially the same as the urea fed group (Group 2) . Based on this single study it appears that urea fed as a urea-fatty acid complex is efficiently utilized. No well-conducted repeated dose toxicity studies on urea were located (UNEP, date and RL not specified) . Chronic toxicity and carcinogenicity screening studies in mice and rats fed with 4500, 9000 or 45000 ppmin diet (up to about 6750 mg/kg body weight/day for mice and about 2250 mg/kg body weight/day for rats) did not uncover any treatment-related toxic syndromes in the various organs studied (Fleischman et al ., 1980, RL not specified) . Neither was any weight depression noted at terminal necropsy for animals of either sex or species at any dose levels. Thus the NOAELs were about 6750 mg/kg body weight/day for mice and about 2250 mg/kg body weight/day for rats. Repeated dose toxicity studies with rats by skin application over 4 weeks and 25 weeks were conducted using urea ointment at 10%, 20% and 40%concentrations, and no consistent treatmentrelated toxic effects were found. The ointments were applied on a 20 cm2area of the back skin but, unfortunately, the quantities of urea applied were not given. Therefore no value for NOAEL by dermal route can be determined. It can be concluded, however, that the repeated dose toxicity of urea by dermal route was low(UNEP, date and RL notspecified) .UREA, REACTION PRODUCTS WITH FORMALDEHYDE

Table 3 Summary of repeated dose toxicity: Urea* Study Design Result RL/Reference Pullets; diet: 0, 1 %urea, 1% biuret, or soybean oil - NOAEL = 1%urea 2/ Berry et al ., 1956 exposure time not specified Lambs; diet: 7.5%cottonseed meal (Group 1), 1% NOAEL =1% urea 2/ Berry et al ., 1956 cottonseed meal plus 1% urea feed-urea (Group 2), 1% cottonseed plus 1%

crude biuret (Group 3) - 84 d Steers; diet: 7.5%cottonseed meal (Group 1), 1% NOAEL =1%urea 2/ Berry et al ., 1956 feed-urea (Group 2), 1% crude biuret (Group 3), 1 .5% a mixture of crude biuret and feed-urea (Group 4), and 1 .25%of a urea-fatty acid complex (Group 5) - 84 days Rat or mouse; diet : 4500, 9000or 45000 ppm - 12 m NOAEL (mouse) ca. = Not

6750mg/kg bw/day; (rat) specified/Fleischman ca. = 250 mg/kg bw/day et al ., 1980 Rat ; dermal : 10%, 20%

and 40%- 4 or 25 w NOAEL not identified. Not specified/ Not Repeated dose toxicity specified; UNEP, date "low" not specified (*) The Berry et al ., 1956 studies presented in Table 2were not included in the SIDS documents for Urea. 3.1 .4 Mutagenicity Mutagenicity studies were not located for UF. Urea has been tested for mutagenicity in vitro and in vivo. The mechanismof genotoxicity of urea is probably non-specific (e.g. difference in osmotic pressure across the cell membrane) (UNEP, no date specified) . Similar effects are expected for UF. In vivo Studies Urea was clastogenic for mammalian cells in vivo but the interpretation of this clastogenic effect is limited by the usage of a single extremely high dose level (Chaurasia and Sinha, 1987, RL not specified) . In vitro Studies Urea has been negative in several appropriately conducted bacterial mutagenicity tests (Ishdate, et al, 1981 ; Shimizu et al ., 1985; Mortelmans et al ., 1986, RL notspecified) . Urea caused DNAsingle strand breaks in mammalian cells in mouse lymphoma cells (Garberg et al ., 1988, RL not specified) but not rat hepatocytes (Sina et al ., 1984, RLnot specified) . Urea was clastogenic in a Mouse Lymphoma TK Locus Assay ; but only at concentrations much beyond the physiological range (about 50-100 higher concentrations than found in human blood) (Wangenhaim . and Bolcsfoldi, 1988, RL not specified) . The positive genotoxic findings may depend on secondary cellular effects (e.g. difference in osmotic pressure across the cell membrane) at high concentration which might not take place under in vivo conditions. The maximally effective concentration or production of chromosome aberrations in Chinese hamster fibroblast cells was 266 mmolar, a very high concentration suggesting a low clastogenic potential (Ishidate and Odashima, 1977, RL not specified) . Chromosomal aberrations were detected in 20%of metaphases of Chinese hamster fibroblast cells at urea concentration of 13 g/L (216 mmolar) indicate a lowclastogenic potential (Ishdate et al . 1981, RL not specified) . The mechanismof genotoxicity is probably non-specific (e.g. difference in osmotic pressure across the cell membrane) .

I1

### UREA, REACTION PRODUCTS WTTH FORMALDEHYDE

3.1.5 Toxicity for Reproduction Standard reproductive toxicity studies have not been conducted with UF or urea. Urea is an important endogenous product of mammalian metabolism . This may partly explain why it has not been rigorously studied with toxicological tests. Nevertheless, urea appears to cause little or no toxicity to most manunalian species (ruminants are an exception) and humans at reasonable dose levels (UNEP, no date specified) . Effects on Fertility The studies cited under repeated dose toxicity for urea did not indicate any toxic effects on the reproductive organs of mice and rats. No NOAEL can be given for the reproductive/developmental toxicity of urea because appropriate studies are lacking (UNEP, no date specified) . Developmental Toxicity No adequate teratogenicity/developmental toxicity studies of urea with mammals were located. According to one rat study, 50g/kg body weight/day administered by gavage in two doses 12 hours apart for an average of 14 days did not cause outstanding (external) teratogenicity; the mean birth weight of the newborn was lower but the litter size greater. Injection of urea into the air sack of eggs shows that urea is toxic to the development ofchick embryo (UNEP, no date specified) . 4 HAZARDS TOTHE ENVIRONMENT 4.1 Aquatic Effects Acute aquatic toxicity studies were not located for UF; data on urea is expected to be representative of UF based on its degradation to urea, carbon dioxide and ammonia . Urea has generally low acute ecotoxicity to organisms. The degradation product of urea, ammonia, is known to be toxic to all vertebrates. In neutral and acidic conditions, however, ammonia exists in the formof ammonium . Instead of toxic effects, more emphasis should be put on the indirect influence of urea to the environment via eutrophication and the pollution risk of urea to groundwater, when urea is used as a fertilizer and a deicer agent in airports. Also the long-term influence of urea use e .g. soil acidification after the long-termfertilization and ammonia emissions to air can have influence to the whole ecosystemand should be considered (UNEP, no date specified) . AcuteToxicity Test Results Urea is not acutely toxic to fish, algae or aquatic invertebrates. Examples of published data include an LC50 for 96 hours > 9100 mg/L for Barilius barna (Dodriyal and Bahuguna, 1988, RL not specified) ; a toxicity threshold for 192 hours > 10000 mg/L for Scenedesmus quadricauda (Bringmann and Kuhn, 1978, RL not specified) and an EC50 for 24 hours > 10000 mg/L for Daphnia magna (Bringmann and Kuhn, 1982, RL not specified) . 

### 5 RECOMMENDATIONS Additional testing is not required for UF. The existing or modelled data for UF in combination with published data on urea provides acomplete profile for this substance.

12

### UREA, REACTION PRODUCTS WITH FORMALDEHYDE

6 REFERENCES Berry, W

.T., Riggs, J .K

., and Kunkel, H

.O . (1956) The lack oftoxicity ofbiuret to animals. Journal ofAnimal Sciences 15:225. Bringmann, G

. and Kuhn, R

. (1978) Vom

Wasser, 50, 45-60, (1978) as cited in OECD/SIDS. Screening Information Data Set (SIDS) ofOECDHigh Production Volume Chemicals Programme, (1994) Bringmann, G

. and Kuhn, R

. (1982) Zeitschrift fuer Wasser und Abwasser Forschung, 15(1), 1-6, (1982) as cited in OECD/SIDS. Screening Information Data Set (SIDS) ofOECD High Production Volume Chemicals Programme, (1994) Chaurasia, O

. P . and Sinha, S. P

. (1987) Cytologia, 52, 877-882, (1987) as cited in OECD/SIDS . Screening Information Data Set (SIDS) of OECDHigh Production Volume Chemicals Programme, (1994) Dodriyal, A

. K . and Bahuguna, A

. K . Himalayan (1988) Chemical Pharma. Bulletin, 5, 15-16, (1988) as cited in OECD/SIDS. Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) The Fertilizer Institute (2007) Personal Communication with William Herz, Vice President, Scientific Programs, TFI, Washington, DC . Fleischman, R

. W . et al . Journal of Environmental Pathology and Toxicology, 3(5/6), 149-170, (1980) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) Fonnesbeck, P.V

., Kearl, L.C. and Harris, L .E. (1975) Feed Grade Biuret as a Protein Replacement for Ruminants. Journal of Animal Science, vol 40, no. 6, pp. 1150-1184 . FDA (US-Food and Drug Admin.) (1978) Health Hazard Evaluation Determination Report, PB288673, (1978) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) Garberg, P

. et al . (1988) Mutation Research, 203, 155-176, (1988) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) Hays JT and Haden WW (1966) Soluble fraction of ureaform- nitrification, leaching and burning. J Ag Food Chem

Vol 14 No 4 pp 339-341 . Ishidate, M

. and Odashima, S. (1977) Mutation Research, 48, 337-354, (1977) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) . Ishidate, M

. et al . (1981) GANN Monograph on Cancer Research, 27, 95-108, (1981)as cited in OECD/SIDS Screening Information Data Set (SIDS) ofOECDHigh Production Volume Chemicals Programme, (1994) .

13

### UREA, REACTION PRODUCTS WITH FO RMALDEHYDE Jahns, T and Kaltswasser, H (2000) Mechanismof Microbial Degradation of Slow Release Fertilizers, Journal of Polymers and the Environment V8 No 1, pp 11-16 . Kaempffe GC and Lunt OR (1967) Availability of various fractions of urea-formaldehyde. J Agr Food Chem

V15 No 6 pp 967-971 . Katz, SE and Fassbender, CA (1966) Biodegradability of Ureaformaldehydes and Related Compounds. J Agr and Food Chemistry V14, No 4pp 336-339 . Long and Winsor (1960) as cited in Kaempffe and Lunt (1967) . Mortelmans, K

. et al . (1986) Environmental Mutagenesis, 8 Suppl . 7, 1-119, (1986) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) . 

### Murray, T.P., Austin, E.R., Howard, R.G ., and Horn R

.C. Anal . Chem

., vol 54, 1505, 1982

. Sato, N . et al . Oyo Yakuri (1978) (Pharmacometrics), 13, 749-772, (1978) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) . Shimizu, H

. et al . (1985) Japanese Journal of Industrial Health, 27, 400-419, (1985) as cited in OECD/SIDS Screening Information Data Set (SIDS) ofOECDHigh Production Volume Chemicals Programme, (1994) . Sina, J. F. et al . (1984) Mutation Research, 113, 357-391, (1984) as cited in OECD/SIDS Screening Information Data Set (SIDS) ofOECD High Production Volume Chemicals Programme, (1994) . USEPA (no date specified) AP 42, Fifth Edition, Volume I Chapter 8 : Inorganic Chemical Industry http://wwwepa gov/ttn/chief/ap42/ch08/final/c08s02.ndf . UNEP Publications (date notspecifed) OECDSIDS, Urea. Wangenhaim, J . and Bolcsfoldi, G . Mutagenesis, 3, 193-205, (1988) as cited in OECD/SIDS Screening Information Data Set (SIDS) of OECD High Production Volume Chemicals Programme, (1994) .

# IU CLID

Data Set Existing Chemical : ID: 68611-643 CAS No . : 68611-64-3 EINECS Name : Urea, reaction products with formaldehyde EC No . : 271-898-1 Producer related part 

### Company : Epona Associates, LLC Creation date : 28.06.2007 Substance related part , Company : Epona Associates, LLC Creation date : 28.06 .2007 Status . Memo : TFI 

### Printing date : 29.02.2008 Revision date . Date of last update : 29.02.2008 Number of pages : 32 Chapter (profile) : Chapter: 1, 2, 3, 4, 5, 6, 7, 8, 10 Reliability (profile) : Reliability: without reliability, 1, 2, 3, 4 

### Flags (profile) : Flags: without flag, confidential, non confidential, WGK (DE), TA-Luft (DE), Material Safety Dataset, Risk Assessment, Directive 67/548/EEC, SIDS

### p. 1



## 1 . General Information

1 .0.1 APPLICANT ANDCOMPANYINFORMATION 1 .0.2 LOCATION OF PRODUCTION SITE, IMPORTER OR FORMULATOR 

### 1 .0.3 IDENTITY OF RECIPIENTS 1 .0.4 DETAILSON CATEGORY/TEM PLATE 

### Id 68611-64-3 Date 29.02.2008

Comment : Urea, reaction products with formaldehyde is represented by methylene diurea Remark



### 28.06.2007 In summary, although this is a complex and variable mixture, enough is known about its chemistry and overall composition to derive a well-informed hazard characterization based on adequate studies of components and degradation products. MDU is the primary component of CAS No 68611-64-3 and was selected, using scientific rationale, as the most representative material with sufficient data that would be an adequate surrogate to represent this variable mixture . Slow-release, or ureaform, fertilizers are produced fromthe reaction of urea, formaldehyde, sodiumhydroxide and water. Ureaform reaction is initiated by the addition of acid, forming a wide distribution of methyleneurea polymers, the lowest member of the polymers is methylenediurea (MDU; CAS No 13547-17-6) . MDU, the smallest member of the methyleneurea polymers series, is used as a structural analogue to represent the population of larger polymeric methyleneurea polymers as described by CAS No 68611-64-3. In addition, MDUis the largest component of the methyleneurea polymers found in ureaformfertlizers. Comment : Urea, reaction products with formaldehyde is represented by methylene diurea Remark : MDU is the principle compound formed when the formaldehyde additive reacts with hot urea . 10.07.2007 (13) (19) Comment : Urea, reaction products with formaldehyde is represented by methylene diurea 

### Remark 29.02.2008 Isopropyl methylenediurea (CAS No . 6104-30-9

; chemical name 1,1'-(2- methylpropane-1,1-diyl)diurea) isconsidered to-b~:an3a~log_of MDU . The only difference between themis the substitutioiiofi isop~~opjrl for Hon the methylene carbon. 1 .1 .0 SUBSTANCE IDENTIFICATION IUPAC Name . Urea, reaction products with formaldehyde Smiles Code . Molecular formula . Unknown, Variable, Complex, Biological 2/32

### p. 16



## 1 . General Information Molecular weight Petrol class Id 68611-64-3 Date 29.02.2008



### Remark : Urea, reaction products with formaldehyde (CAS NO 68611-64-3) is an indeterminate mixture of variable composition derived as a byproduct froma chemical process. To understand how

this material relates to other chemicals that have relevant data and to appreciate the potential range of various components, it is useful to comprehend the process and process variables that contribute to the production of this byproduct mixture . 28.06.2007 

### 1 .1 .1 GENERAL SUBSTANCE INFORMATION Purity type : typical for marketed substance Substance type . Physical status . Purity . Colour . Odour . Remark : CAS 68611-64-3 is not manufactured or processed for

28.06.2007 distribution in commerce as chemical substances per se and, relative to the fertilizer industry, have no commercial purpose separate fromthe substance mixture or article of which they may be a part (40 CFR§ 710 .4(d) . 

### Fertilizer grade ureaformis composed primarily of a mixture of straight chain polymers of urea and formadlehyde containing as many as 6 urea residues. Slow-release, or ureaform, fertilizers are produced fromthe reaction of urea, formaldehyde, sodiumhydroxide and water . Ureaformreaction is initiated by the addition of acid, forming a wide distribution of methyleneurea polymers, the lowest member is methylenediurea. Thefinal product contains unreacted urea, methylenediurea, methylenetriurea and longer chain polymers. Purity type : typical for marketed substance Substance type . Physical status . Purity . Colour . Odour . 

### Remark : Fertilizer grade ureaformis composed primarily of a mixture 28.06.2007 1 .1 .2 SPECTRA 

### of straight chain polymers of urea and formaldehyde containing as many as 6 urea residues.

1 .2 SYNONYMSANDTRADENAMES (7) (14)



### (3) (9)

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### p. 17



## 1 . General Information 1 .3 IMPURITIES 1 .4 ADDITIVES 

### 1 .5 TOTAL QUANTITY Quantity Remark

09.07.2007 

### 1 .6 .1 LABELLING 1 .6.2 CLASSIFICATION 1 .6 .3 PACKAGING 1 .7 USE PATTERN 0 - tonnes in 2005 Id 68611-643 Date 29.02.2008

Urea, reaction products with formaldehyde, as represented by MDU, is considered an impurity of urea with no commercial purpose for reporting underTSCA Section 8 Inventory Update Reporting (IUR), is not manufactured or processed for distribution in commerce as a chemical substances per se and, relative to the fertilizer industry, has no commercial purpose separate fromthe substance mixture or article of which they may be a part (40 CFR § 710 .4(d)

. MDU is not a commercial product; it is produced incidentally during the production of urea fertilizers and as such is not reportable under the Inventory reporting Rule. The members of The Fertilizer Institute are not Tier 1 producers of MDU

Type of use ; use 

### Category Remark : Urea Reaction r d t M, f 10.07.2007 , p o uc swi ormaldehyde, as represented by MDUis produced incidentally in the production of urea fertilizers; it is not produced commercially by the members of The Fertilizer Institute . Type of use : use 

### Category Remark On April 15, 2002, the Environmental Protection Agency (EPA) issued its tolerance reassessment decision for the frost protectant pesticide urea, and is inviting public comment until May 15, 2002. EPAfinds that urea poses no risk concerns within the limits of the existing tolerance exemptions. Therefore, no additional risk mitigation is needed, and no changeswill be made to the 78 urea tolerance exemptions as a result of this reassessment decision. EPA regards the 78 exemptions as completed tolerance 

### (15)

(15)

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### p. 18



# 1 . General Information Id 68611-643 Date 29.02.2008 reassessments, contributing toward the Agency's goal of completing 66%

of all required tolerance reassessment decisions by August 3, 2002. 

### A naturally occurring compound in humans, urea is approved for several human therapeutic uses. In addition, urea is considered "Generally Recognized As Safe" (GRAS) as affirmed by the U. S. Food and Drug Administration for use in food. Urea is an active ingredient in only one registered pesticide product, Enfrost, which is registered for commercial application to a wide variety of field crops, vegetables, fruit trees, and ornamentals to reduce frost formation by ice-nucleating bacteria naturally present on leaf surfaces. Urea also is an inert ingredient included in pesticide products as a stabilizer, inhibitor, or intensifier. Outside the pesticide realm, urea is included in fertilizer, used as an animal feed supplement, and used in the manufacture of dyes, fire retardant paints, plasticizers, and stabilizers for explosives. The Federal Register notice is available on EPA'swebsite at http://www

.epa.gov/fedrgstr. Risk assessments and related documentsfor urea also are available at http://www

.epa.gov/oppsrrd1 /reregistration/urea/. 

### Test substance : Urea 09 .07.2007 (17) Type of use : use Category . Remark : 21 C .F.R. § 184

.1923 Urea. Title 21 - Food and Drugs 

### Title 21 : Food and Drugs PART 184-DIRECT FOODSUBSTANCES AFFIRMEDAS GENERALLY RECOGNIZEDAS SAFE Subpart B-Listing of Specific Substances Affirmed as GRAS Browse Previous I Browse Next § 184.1923 Urea . (a) Urea (CO(NH2)2, CAS Reg. No. 57-13-6) is the diamide of carbonic acid and is also known as carbamide. It is a white, odorless solid and is commonly produced from C02 by ammonolysis or fromcyanamide by hydrolysis. 

### (b) FDA is developing food-grade specifications for urea in cooperation with the National Academy of Sciences. In the interim, this ingredient must be of a purity suitable for its intended use. (c) In accordance with §184.1(bx1), the ingredient is used in food with no limitation other than current good manufacturing practice. The affirmation of this ingredient as generally recognized as safe as a direct human food ingredient is based upon the following current good manufacturing practice conditions of use : (1) The ingredient is used as a formulation aid as defined in §170.3(o)(14) of this chapter and as a fermentation aid. (2) The ingredient is used in yeast-raised bakery products; in alcoholic beverages as defined in §170.3(n)(2) of this chapter; and in gelatin products. (d) Prior sanctions for this ingredient different fromthe uses established in this section do not exist or have been waived. [48 FR 51616, Nov. 10, 1983, as amended at 49 FR 19816, May 10,1984] 

### Test substance : Urea 5/32

### p. 19



## 1 . General Information Id 68611-643 Date 29.02.2008 09.07.2007 (16) Type of use : use Category . Remark : Urea is approved for several therapeutic uses in humans with relatively few

toxicities. Urea is used primarily as an 

### osmotic agent for inducing diuresis and reducing intraoccular and intracranial pressure. Urea has also been used as a topical anesthetic for the treatment of mouth and throat inflammation (10-15%urea gel, liquid or solution), to debride necrotic and infected tissues, i .e. fingernails and toenails. It is also used in the treatment of sicklecell anemia and to ammoniate dentrifices as well as a basic ingredient in the synthesis of medically important compounds such as barbiturates and urethanes . http://www

.epa .gov/oppsrrd1/REDs/urea tred .htm; http://216.239.51 .104/search?q=cache:p-1264Z8FFIJ :www .fda.go vcder/ogd/rld/12154s24 .pdf+FDA+category+C+urea&hl=en&ct=clnk &d=1 &gl=us Test substance : Urea 09 .07.2007 

### 1 .7.'1 DfTAfLED-USE PATTERN 1 .7.2 METHODS OF MANUFACTURE Origin of substance : Polymer Type : Production 

### Remark Slow-release, or ureaform, fertilizers are produced fromthe reaction of urea, formaldehyde, sodiumhydroxide and water. Ureaform reaction is initiated by theaddition of acid, forming a wide distribution of methyleneurea polymers, the lowest member of the polymers is methylenediurea (MDU; CAS No 13547-17-6)

. MDU, the smallest member of the methyleneurea polymers series, is used as a structural anlog to represent the population of larger polymeric methyleneurea polymers as described by CAS No 68611-64-3. In addition, MDU is the largest component of the methyleneurea polymers found in ureaformfertlizers. 

### Urea reaction products are formed when formaldehyde-based additives (FBA) are added to the hot urea (apx. 280o F) process at lowconcentration. FBAimmediately and essentially irreversibly reacts to formmethyleneureas, at which point the formaldehyde loses its chemical identity. The principal reaction product in the resulting urea product is methylenediurea (MDU) . In the presence of strong acids, the reaction does not stop at MDU, but rather forms methyleneurea polymers. Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. Whilethis discussion will focus primarily on MDU, additional data are presented for other methyleneurea polymers. 

### (18)

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### p. 20



## 1 . General Information Id 68611-64-3 Date 29.02.2008 Urea, reaction products with formaldehyde (CAS NO 68611-64-3) is an indeterminate mixture of variable composition derived as a byproduct froma chemical process. To understand how

this material relates to other chemicals that have relevant data and to appreciate the potential range of various components, it is useful to comprehend the process and processvariables that contribute to the production of this byproduct mixture . 

### 28.06.2007 1 .8 REGULATORY MEASURES Remark Fertilizers, fertilizer materials, and their manufacturing facilities are highly regulated at the federal and state level . At the federal level, standards are in place to govem : (I) air emissions fromfertilizer and fertilizer material manufacturing facilities [These regulations are found at: (1) 40 C.F.R. Part 60, Subpart G (standards of performance for nitric acid plants) ; (2) 40 C

.F.R. Part 60, Subpart H (standards of performance for sulfuric acid plants); (3) 40 C .F .R. Part 60, Subpart T (standards of performance for wet process phosphoric acid plants) ; (4) 40 C .F .R. Part 60, Subpart U (standards of performance for superphosphoric acid plants) ; (5) 40 C .F .R. Part 60, Subpart V(standards of performancefor diammoniumphosphate plants); (6) 40 C .F.R. Part 60, Subpart W

(standards of performance for triple superphosphate plants) ; (7) 40 C .F.R. Part 60, Subpart X (standards of performancefor granular triple supetphosphate storage facilities) ; (8) 40 C .F.R. Part 60, Subpart NN (standards of performance for phosphate rock plants) ; (9) 40 C

.F .R. Part 60, Subpart PP (standards of performancefor ammoniumsulfate plants); (10) 40 C .F .R. Part 61, Subpart R(national emission standards for radon emissions ftomphosphogypsumstacks) ; (11) 40 C .F .R.] ; (2) solid and hazardouswaste generation, storage, transportation, and disposal [40 C .F .R. §§ 260-299

.] ; (3) water discharges [40 C .F.R. Part 122.]; (4) accident prevention and mitijation [40 C .F.R. Part 68 and 29 C .F .R . § 1910.119

.] ; (5) release reporting [40 C .F .R. §§ 302.4, 355 .40and 40 C.F .R

. Part 372

. ] ; (6) worker exposure [29 C .F.R. §§ 1910.1000and 1910.1020 .] ; (7) hazard communication [29 C

.F.R. § 1910.1200] ; and 

### (8) transportation [49 C

.F.R.SubchapterC] . These regulations provide a comprehensive federal programto regulate fertilizers and fertilizer materials. In addition, and without conceding any arguments that could be made to the contrary, TSCA§ 6provides EPAwith the authority to either prohibit or limit the manufacture of a chemical substance upon a finding that its manufacture, processing, distribution in commerce, use, or disposal "presents or will present an unreasonable risk of injury to health or theenvironment ." Also, underTSCA § 7, the Agency has the authority to take certain actions in response to an "imminently hazardous chemical substance or mixture." In addition to federal regulations, the states regulate fertilizers and fertilizer materials. As noted in the attached document, entitled Summary of State Fertilizer Laws, 48 states have laws and



### 7/32

### p. 21



## 1 . General Information

09.07.2007 Id 68611-643 Date 29.02.2008 regulations in place to regulate fertilizers and fertilizers materials. Many of these states have an "adulteration" clause in their laws that enable the responsible state agency to stop the sale of fertilizers and fertilizer materials that are dangerous to human health. Notably, five states have adopted comprehensive regulations to limit the amounts of nonnutritive elements in fertilizers. Thesestates are Washington, California, Oregon, Florida and Texas. EPA, in response to a congressional inquiry, endorsed these programs. Otherstates are developing similar regulations fostered by the work of theAssociation 

### ofAmerican Plant Food Control Officials (AAPFCO) . 1 .8.1 OCCUPATIONAL EXPOSURE LIMIT VALUES 1 .8.2 ACCEPTABLE RESIDUES LEVELS 1 .8 .3 WATERPOLLUTION 1 .8 .4 ACCH)ENT' HAZARDS 1 .8.5 AIR POLLUTION 1 .8 .6 LISTINGS E.G. CHEMICAL INVENTORIES 1 .9 .1 DEGRADATION/TRANSFORMATION PRODUCTS 1 .9 .2 COMPONENTS 1 .10 SOURCE OF EXPOSURE 1 .11 ADDITIONAL REMARKS 1 .12 LAST LITERATURE SEARCH 1 .13 REVIEWS

8/32

### p. 22



## 2 . Physico-Chemical Data

2.1 MELTING POINT Value . 212 - 214 °C Sublimation . Method : other: melting point block Year : 1966 GLP : no Test substance : other TS: MDU 

### Id 68611-64-3 Date 29.02.2008

Method : The crude product was slurried with methanol, cooled to 40 C and filtered warm

. The filtrate was held at OCfor 16hours and the crytalline product filtered off (MP = 213C) . Because of the heat sensitivity of MDU and Dimethyleneurea (DMU) the sample had to be droppped on a melting point block heated to within about 5Cof the final melting point to get complete melting. The melting points quoted were taken in this manner. The extraction procedurewas rpeated until the melting point began to increase . In this way, 70%

of crude product was isolated as sharp melting crystals (212-214 C) . Reliability : (2) valid with restrictions Published information 28.06.2007 

### 2 .2 BOILING POINT Decomposition Method 

### Year GLP Test substance 2007 no as prescribed by 1 .1 - 1 .4 Remark : The substance is a solid; BP is not appropriate Reliability : (2)valid with restrictions 

### Technical discussion regarding physical properties 28.06.2007 2.3 DENSITY 2 .3 .1 GRANULOMETRY 2A VAPOUR PRESSURE Decomposition Method Year GLP Test substance Remark Reliability 28.06.2007 2007 no as prescribed by 1 .1 - 1 .4 

### The substance is a solid; VP is not appropriate (2) valid with restrictions Technical discussion regarding physical properties (5)

9/32

### p. 23



# 2. Physico-Chemical Data

2.5 PARTITION COEFFICIENT Partition coefficient : octanol-water Log pow . -3.01 at °C pH value . Method : other (calculated) Year : 2007 

### GLP : no Test substance : other TS: MDU Method : KOWWIN Program(v1 .67) :

------------------------------- ------------------------------- SMILES : 0=C(NCNC(=0)N)N CHEM : Urea, N,N"-methylenebisMOL FOR

: C3 H8 N4 02 

### MOL WT : 132.12 Id 68611-64-3 Date 29 .02.2008

Physical Property Inputs: Water Solubility (mg/L) : 25000 Vapor Pressure (mmHg) : ------ Henry LC (atm-m3/mole) : ----- Log Kow(octanol-water) : ------ Boiling Point (deg C) : ------ Melting Point (deg C) : 212.00 

### Remark : CAS 68611-64-3 is UCVB; modeling is not appropriate Result : KOWWIN Program(v1 .67) Results:

------------------------------- -------------------------------

Log Kow(version 1 .67 estimate) : -3.01 ----+---------+------- TYPE I NUM

I LOGKOW

FRAGMENT DESCRIPTION COEFF I VALUE -------+-----+---------------------------------------+- -------+------- Frag ~ 1 1 -CH2- [aliphatic carbon] 0.4911 1 0.4911 Frag ~ 2 1 -NH2 [aliphatic attach] 1-1 .4148 1-2.8296 

### Frag 1 2 1 -NH- [aliphatic attach] 1-1 .4962 1-2.9924 Frag 1 2 1 -NC(=0)N- [urea] 1 .0453 ~ 2.0906 Const ~ I Equation Constant 1 0.2290 -------+-----+----------------------------------------+- -------+-------- Log Kow = -3.0113 Reliability : (2) valid with restrictions Modeled data 28.06.2007 (4) 

### 2 .6.1 SOLUBILITY IN DIFFERENT MEDIA Solubility in : Water Value . 25 g/I at 25 °C pH value . 10/32

### p. 24



## 2 . Physico-Chemical Data concentration . at °C Temperature effects . Examine different pol . . pKa : at 25 °C 

### Description . Stable . Deg. product . Method : other Year : 1966 GLP : no Test substance : other TS: MDU 

### Id 68611-64-3 Date 29.02.2008

Remark : The water solubility of dimethylenetriurea at 25Cwas 1 g/L. Result : 70 g/L at 50C Reliability : (2) valid with restrictions Published information 

### 28.06.2007 2 .6.2 SURFACE TENSION 2.7 FLASH POINT 2.8 AUTO FLAMMABILITY 2.9 FLAMMABILITY 2.10 EXPLOSIVE PROPERTIES 2.11 OXIDIZING PROPERTIES 2.12 DISSOCIATION CONSTANT 2.13 VISCOSITY 2.14 ADDITIONAL REMARKS (5)

11/32

### p. 25



# 3. Environmental Fate and Pathways

3 .1 .1 PHOTODEGRADATION Type Light source Light spectrum Relative intensity INDIRECT PHOTOLYSIS Sensitizer 

### Conc. of sensitizer Rate constant Degradation Deg. product Method Year GLP Test substance Method



### Remark Result . air : Sun light

. nm

. based on intensity of sunlight : OH : 5000 molecule/cm'

. .00000000000197 cm'/(molecule*sec)

. 50 %after .5 day(s) other (calculated) 2007 no other TS: MDU Id 68611-64-3 Date 29.02.2008

AOP Program(v1 .92) SMILES : 0=C(NCNC(=0)N)N CHEM : Urea, N,N"-methylenebisMOL FOR

: C3 H8 N4 02 

### MOL WT : 132.12 CAS 68611-64-3 is UCVB; modeling is not appropriate AOP Program(v1 .92) Results:

--------------------------- --------------------------- --- SUMMARY (AOP v1 .92) : HYDROXYL RADICALS Hydrogen Abstraction = 15.7005 E-12 cm3/molecule-sec **Reaction with N, S and -OH = 4 .0000 E-12 cm3/molecule-sec Addition to Triple Bonds = 0.0000 E-12 cm3/molecule-sec Addition to Olefinic Bonds= 0.0000 E-12 cm3/molecule-sec Addition to Aromatic Rings= 0.0000 E-12 cm3/molecule-sec Addition to Fused Rings = 0.0000 E-12 cm3/molecule-sec OVERALL OH Rate Constant = 19.7005 E-12 cm3/molecule-sec HALF-LIFE= 0

.543 Days (12-hr day; 1 .5E6 OH/cm3) HALF-LIFE = 6

.515 Hrs



### .. . .. . .. . .. .. . .. .. .. . .. . ** Designates Estimation(s) Using ASSUMED Value(s) ------------------ SUMMARY (AOP v1 .91) : OZONE REACTION 

### ****** NOOZONE REACTION ESTIMATION ****** (ONLY Olefins and Acetylenes are Estimated)

Reliability 28.06.2007 Experimental Database: NOStructure Matches Fraction sorbed to airborne particulates (phi): 0 .00474 (Junge,Mackay) Note: the sorbed fraction may be resistant to atmospheric oxidation : (2) valid with restrictions Modeled data 

### (4)

12/32

### p. 26



## 3 . Environmental Fate and Pathways 3.1 .2 STABILITY IN WATER Type : abiotic t1/2 pH4 . at °C t1/2 pH7 . at °C t1/2 pH9 . at °C 

### Degradation . 50 % after 1 year at pH and °C Deg. product . Method : other (calculated) Year : 2007 

### GLP : no Test substance : other TS: MDU Method

Remark Result 

### Id 68611-64-3 Date 29.02.2008

HYDROWIN Program(v1 .67) SMILES : 0=C(NCNC(=0)N)N CHEM : Urea, N,N"-methylenebisMOL FOR: C3 H8 N4 02 MOL WT : 132.12 Physical Property Inputs: Water Solubility (mg/L) : 25000 Vapor Pressure (mmHg) : ------ Henry LC (atm-m3/mole) : ------ Log Kow(octanol-water) : ------ Boiling Point (deg C) : ------ Melting Point (deg C) : 212.00 CAS 68611-64-3 is UCVB; modeling is not appropriate HYDROWIN Program(v1 .67) Results :

-------------------------------- -------------------------------- ------- HYD

ROW I N v1 .67 Results ------------------------- 

### UREA: -N-C(=0)-NCompound has a urea group; C=0 located at SMILES atom#: 2 Hydrolysis Rate Extremely Slow or t1/2 > 1 Year ***** CALCULATION NOT PERFORMED ***** UREA: -N-C(=0)-NCompound has a urea group; C=0 located at SMILES atom# : 6 Hydrolysis Rate Extremely Slow or t1/2 > 1 Year ***** CALCULATION NOT PERFORMED Reliability : (2) valid with restrictions 

### Modeled data ***** 09.07.2007 (4) 3.1 .3 STABILITY IN SOIL Type : laboratory Radiolabel : no Concentration . Soil temperature . °C Soil humidity . Soil classification . Year . Deg. product . Method : other Year : 1966 GLP : no 

### 13/32

### p. 27



## 3 . Environmental Fate and Pathways Test substance : other TS: MDU, DDU Id 68611-64-3 Date 29 .02.2008

Method : Procedure described in Clark, KG, Yee, JT, Lundstrom, FO, Lamont, TG

. (1959) J Assoc Offic Agr Chemists 42, 596and in Hays JT, Haden, WW and Anderson, LE (1965) J Agr Food Chemists, 13, 176

. Result : Negligible nitrification occurred in the first eight days on reference soil . Urea reached 80%conversion to nitrate after 12 days, MDU nitrification was slower (about 30%in 12 days; 90%

in 14 days) and dimethylene dinitriurea (DDU) nitrification was slower still (about 15% in 12 days; 50%in 14 days) . 

### In a second experiment, water was added to the soil 10 days before the addition of the test substances to allowthe build-up of nitrifying bacteria. The induction period was nearly eliminated for urea (100%in 8 days), while MDU and DDU required 8 or 9 days to begin production of significant amounts (after 16 days about 90% for MDU and about 30% for DDU) of nitrate. Conclusion : The rates of nitrification of the methyleneureas are clearly slower than urea; there appears to be about a week delay 

### before nitrification of the nonurea, soluble ureaform components begin, and the subsequent rate is dependent on molecular weight. 

### Reliability : (2) valid with restrictions Published information 10.07.2007 Type : laboratory Radiolabel . Concentration . Soil temperature . °C Soil humidity . Soil classification . Year . Deg. product . Method : other Year : 1960 GLP : no 

### Test substance : other TS: MDU and DDU (5)

Result : 85%nitrification of MDU and DDU was observed in three weeks; 68%of trimethylene tetraurea and <5%tetramethylene pentaurea was observed in the same period. Reliability : (4) not assignable 

### Original article not reviewed 10.07.2007 (9) (11) Type : laboratory Radiolabel . Concentration . Soil temperature . °C Soil humidity . Soil classification . Year . Deg. product . Method : other Year : 1967 GLP : no Test substance : other TS: MDU, other polymers 14/32

### p. 28



## 3 . Environmental Fate and Pathways Id 68611-64-3 Date 29.02.2008 Method : To determine if the soluble forms in ureaforms are directly available to the plant, grass was grown and established . Nutrient solutions in which No3, urea, MDU, dimethylene triurea or trimethylene tetraurea were used as sole sources of nitrogen (5, 10, 25, 50 and 100 mM concentrations of nitrogen) in an otherwise nitrogen free solution . Growth responses were measured. Result : Adelay of one week or more was required for response by methylene ureas. Then a rapid oincrease of growth took place, followed by the development of toxic effects and in severe cases, death.



### Reliability 10.07.2007 3.2.1 MONITORING DATA 3.2.2 FIELD STUDIES The response suggests no direct utilization by the plant of the ureaforms or methylenureas as there was a substantial time delay in achieving a normal growth rate. Breakdown of the condensates by internal cleavage of methylene linkages and release of free urea, or exposure and cleavage of internal amino groups resulting in NH4 absorption are suggested mechanisms for utilization of these materials by plants. Solution anlaysis indicates that the observed toxicity effects were probably dueto cleavage to urea molecules and subsequent hydrolysis to ammonia. The relatively high levels of ammonia at the pH levels (pH 4 .5 to 5 .5) produced the toxicity. 

### (2) valid with restrictions Published information

3.3 .1 TRANSPORT BETWEEN ENVIRONMENTAL COMPARTMENTS Type : other: leaching Media : water - soil Air . %(Fugacity Model Level I) Water . %(Fugacity Model Level I) Soil . %(Fugacity Model Level I) Biota . %(Fugacity Model Level II/III) Soil . %(Fugacity Model Level II/III) Method : other Year : 1966 

### Method : Procedure 1 : Asoil fertilizer mixture was added to a column filled with wetted soil . An aspirator was used to draw filtrate through the column, and total nitrigen determined. Procedure 2: Followed the same procedure as 1 above, except the soil was wetted after addition of the fertilizer. Result : Procedure 1 : About 90% of the applied ureaformwas retained in soil ; about 10%of the applied urea was retained in soil . With the more drastic leaching procedure (procedure 2) the retention of ureaform nitrogen was reduced to 76%, due to low solubility. Conclusion : Ureaforms such as MDU and DDU have decreased rates of nitrification and leaching compared to urea. 

### (9)

15/32

### p. 29



# 3. Environmental Fate and Pathways Reliability : (2) valid with restrictions Published information 10.07.2007 Type Media Air Water Soil Biota Soil Method Year Method

Remark Result fugacity model level III 

### % (Fugacity Model Level I) % (Fugacity Model Level I) % (Fugacity Model Level I) % (Fugacity Model Level II/III) % (Fugacity Model Level II/III) other 2007 Id 68611-64-3 Date 29.02.2008

Level III Fugacity Model (Full-Output) :

--------------------------------------- --------------------------------------- ChemName : Urea, N,N"-methylenebisMolecular Wt: 132.12 Henry's LC : 1 .74e-018 atm-m3/mole (Henrywin program) Vapor Press : 2.82e-006 mm Hg (Mpbpwin program) Liquid VP : 0

.000199 mmHg (super-cooled) Melting Pt : 212 deg C (user-entered) Log Kow :-3.01 (Kowwin program) Soil Koc : 0

.000401 (calc by model) 

### CAS 68611-64-3 is UCVB; modeling is not appropriate Level III Fugacity Model (Full-Output) :

--------------------------------------- --------------------------------------- Mass Amount Half-Life Emissions (percent) (hr) (kg/hr) Air 4

.12e-011 13 1000 Water 39 360 1000 Soil 60.9 720 1000 Sediment 0

.0713 3.24e+003 0 

### Fugacity Reaction Advection Reaction Advection

(atm) (kg/hr) (kg/hr) (percent) (percent) 

### Air 1 .32e-021 3.8e-008 7.15e-009 1 .27e-009 2.38e-010 Water 4.46e-023 1 .3e+003 677 43.5 22.6 

### Soil 2.58e-021 1 .02e+003 0 33.9 0 Sediment 4

.08e-023 0.265 0 .0248 0.00883 0.000826 Persistence Time: 579 hr Reaction Time: 748 hr Advection Time: 2.56e+003 hr Percent Reacted: 77 .4 PercentAdvected: 22.6 Half-Lives (hr), (based upon Biowin (Ultimate) and Aopwin) : Air: 13.03 Water: 360 Soil : 720 Sediment : 3240 Biowin estimate: 2.907 (weeks ) (5)

16/32

### p. 30



## 3 . Environmental Fate and Pathways Id 68611-64-3 Date 29.02.2008 Advection Times (hr) : Air: 100 Water: 1000 Sediment : 5e+004 

### Reliability : (2) valid with restrictions Modeled data 28.06.2007 (4) 3.3 .2 DISTRIBUTION 3.4 MODE OF DEGRADATION IN ACTUAL USE 3.5 BIODEGRADATION Type : aerobic trt6eaulum : activated sludge Concentration : 100 mg/I related toTest substance related to Contact time . Degradation . = 78 -100 (t) 0/6 after 1 month Result : readily biodegradable Deg; product . Method : OECDGuide-line 301 C "Ready Biodegradability: Modified MITI Test (I)" Year : 2002 GLP : no data Test substance : other TS Method : Modified MITI test for biodegradation: Test equipment : standard type Test period: 4weeks Chemical concentration: 100 mg/L Concentration "of activated sludge: 30 mg/L Result : IndireoAnalysis: BOD(tVH3) = 78°l0 Direct Analysis: TOC = 90% HPLC =100%a Test substance : 1,1'-(2-methylpropane-1,1-diyl)diurea ('CAS No . 61{)4=30-9

; twllTI No. 2- 1742) (also known as 1,1-DiurbidoFsobutar;+s) :'This chemical is considered to be a valid analog for MDU . From the N `radation perspective, it is similar but in theory might, be slowrsr to degratf6°gisren its substitution (of isopr~yl ;fc~~ ~1) on the methylene carbon. Reliabllity : (Z) validwith restrictions' MITI Database is known to be a reliable source. 29;01242-008 (12) Type : aerobic Inoculum : other: domestic sewage sludge, adapted seed cultures Concentration : 500 mg/I related to Test substance related to Contact time : 7 day(s) Degradation . (t) % after Result . Deg. product . Method : other: modifed Warburg Year : 1966 17/32

### p. 31



# 3. Environmental Fate and Pathways GLP : no Test substance : other TS: MDU's Id 68611-64-3 Date 29.02.2008

Method : Based upon the principles of the BODtest; nitrogen content was made the limiting factor in thetest media Result : Methylenediurea: ca. 80% degradation in 8days, ca. 90% degradation in 14 days. Dimethylenediurea: ca. 70 % degradation in 8and 14 days. Trimethylenetetraurea: 40% degradation in 8days, ca. 60%degradation in 14 days. Low MW fraction degraded 100%in 11 days Intermediate MW

fraction degraded 70%in 11 or after 14 days High MW

fraction degraded <10%in 11 days and ca. 10% after 14 days Combined MW

fractions degraded ca. 66% after 14 days Test substance : Methylenediurea, Dimethylentriurea, Trimethylenetetraurea. Also, the low, intermediate, high and total combined molecular weight fractions of ureaformwere tested. 

### Conclusion : Increases in chain length decrease biodegradability Reliability : (2) valid with restrictions Provides basic data ; uses standard method 29.02.2008 (10) 

### Type : aerobic Inoculum : other: Ralstonia paulcula (garden soil) Contact time . Degradation . (t) %after Result : readily biodegradable Deg. product : yes Method . Year : 2000 GLP : no data Test substance : other TS:MDU and other UF polymers Deg. products . 

### 124-38-9 204-696-9 carbon dioxide 57-13-6 200-315-5 urea Method : Microbial degradation of 7.5mMMDUas the sole source of fixed nitrogen wasfollowed at 26C . 

### Result : Nitrogen was enzymatically released fromthe degradation of methlyenediurea as ammonia and urea, and the formaldehyde released immediately oxidized via formiate tocarbon dioxide. The enzyme is methylenediurease. 100%of the MDUwas degraded by 4 days. Methylenediurea may also be degraded by fungus via the formation of organic acids, thus leading to nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions. 100%MDUwas degraded at 3 days in the presence of Penicilliumnotatum . 

### Reliability : (2) valid with restrictions Published information 29.02.2008 

### Contact time . Degradation . - (t) % after Result : other: likely to biodegrade Deg. product . Method . Year : 2007 GLP : no Test substance : other TS: MDU (7)

18/32

## 3

. Environmental Fate and Pathways Id 68611-64-3 Date 29.02.2008 Method : BIOWIN (v4 .10) Program

------------------------------ ------------------------------ SMILES : 0=C(NCNC(=0)N)N 

### CHEM : Urea, N,N"-methylenebisMOL FOR: C3 H8 N4 02 MOL WT : 132.12 

### Remark : CAS 68611-64-3 is UCVB; modeling is not appropriate Result : BIOWIN (v4 .10) ProgramResults:

----------------------- BIOWIN v4 .10 Results p. 32

Biowin1 (Linear Model Prediction) : Biodegrades Fast Biowin2 (Non-Linear Model Prediction) : Biodegrades Fast Biowin3 (Ultimate Biodegradation Timeframe) : Weeks Biowin4 (Primary Biodegradation Timeframe) : Days-Weeks Biowin5 (MITI Linear Model Prediction) : Does Not Biodegrade Fast 

### Biowin6 (MITI Non-Linear Model Prediction) : Does Not Biodegrade Fast Biowin7 (Anaerobic Model Prediction) : Biodegrades Fast Ready Biodegradability Prediction: NO ------+----+-----------------------------------------+-- ------+-------- TYPE INUM

I Biowin1 FRAGMENT DESCRIPTION COEFF I VALUE ------+----+-------------------------------------------+-- ------+-------- MoIWtj " I Molecular Weight Parameter 

### 1-0.0629 Constj " I Equation Constant 1 0.7475 RESULT I Biowin1 (Linear Biodeg Probability) ( 0.6846

------+-----+-----------------------------------------+-- ------+-------- TYPE INUM

I Biowin2 FRAGMENT DESCRIPTION COEFF I VALUE 

### ------+----+----------------------------------------+-- ------+-------- MoIWtj * I Molecular Weight Parameter 1-1 .8761 ----------__+-_---------------__------------------------- ---------- ----------------- ------------------------- RESULT I Biowin2 (Non-Linear Biodeg Probability) / 0 .7563

A Probability Greater Than or Equal to 0 .5 indicates --> Biodegrades Fast 

### 19/32

### p. 33



# 3. Environmental Fate and Pathways Id 68611-64-3 Date 29.02.2008 A Probability Less Than 0.5 indicates --> Does NOT Biodegrade Fast ------+-----+-------------------------------------+-- ------+-------- TYPE INUM

I Biowin3 FRAGMENT DESCRIPTION COEFF I VALUE ------+-----+--------------------------------------------+-- ------+--------- MoIWtj * I Molecular Weight Parameter 1-0.2920 Constj * I Equation Constant 1 3.1992 

### RESULT I Biowin3 (Survey Model -Ultimate Biodeg) I 1 2.9072

------+----+----------------------------------------+-- ------+-------- TYPE INUM

I Biowin4 FRAGMENT DESCRIPTION COEFF I VALUE ------+----+----------------------------------------+-- ------+-------- MoIWtj * I Molecular Weight Parameter 1-0.1906 Constj * I Equation Constant 1 3.8477 ------------+-_----__-----------______-------__---------- ------------ ------ ----------- ------- ---------- RESULT I Biowin4 (Survey Model -Primary Biodeg) I 1 3.6571 ------------+_________________-----------__-------------- ------------ ----------- -------------- 

### Result Classification: 5.00 -> hours 4.00 -> days 3.00 -> weeks (Primary & Ultimate) 2.00 -> months 1 .00 -> longer ------+----+----------------------------------------+-- ------+--------- TYPE INUM

I Biowin5 FRAGMENT DESCRIPTION COEFF I VALUE ------+-----+------------------------------------------+-- ------+--------- Frag 1 1 1 -CH2- [linear] 0 .0494 1 0

.0494 MoIWtj * I Molecular Weight Parameter 1-0.3931 Constj * I Equation Constant 1 0 .7121 ------------+-_------------------__--------___----__----- ------------ -------------------- -------- ---- ----- RESULT I Biowin5 (MITI Linear Biodeg Probability) I 1 0 .3685 20/32

### p. 34



## 3. Environmental Fate and Pathways

Reliability Id 68611-64-3 Date 29.02.2008

------+----+-----------------------------------------+-- ------+-------- TYPE INUM

I Biowin6 FRAGMENT DESCRIPTION COEFF I VALUE -----+-----+---------------------------------------+-- ------+-------- 

### Frag I 1 I -CH2- [linear] 0.4295 1 0.4295 MoIWtj * I Molecular Weight Parameter 1-3.8142 RESULT jBiowin6 (MITI Non-Linear Biodeg Probability)l 1 0.2975 ------------ ---- 

### A Probability Greater Than or Equal to 0.5 indicates --> Readily Degradable A Probability Less Than 0.5 indicates -> NOT Readily Degradable

------+----+----------------------------------------+-- ------+-------- TYPE INUM

I Biowin7 FRAGMENT DESCRIPTION COEFF I VALUE ------+----+----------------------------------------+-- ------+-------- 

### Frag 1 1 1 -CH2- [linear] 0.0260 ~ 0.0260 Constj * I Equation Constant ~ 0.8361 ------------+_____________------___--------__-----__----- ------------ ------ -------- ----- ----- RESULT I Biowin7 (Anaerobic Linear Biodeg Prob) 1 0.8621



### A Probability Greater Than or Equal to 0.5 indicates --> Biodegrades Fast A Probability Less Than 0.5 indicates -> Does NOT Biodegrade Fast : (2) valid with restrictions Modeled data 29.02.2008 (4) 

### 3.6 13005, CODOR BOD5/COD RATIO

21/32

### p. 35



# 3. Environmental Fate and Pathways 3 .7 BIOACCUMULATION 3.8 ADDITIONAL REMARKS Memo : Mineralization and nitrification 

### Id 68611-64-3 Date 29.02.2008

Method : Three ureaformfertilizers with varying amounts of MDU and free urea were studied for 35 days for mineralization and nitrification in two soil types using 15N and HPLC techniques. Soils were preincubated for 1 month to allow microbial populations to stabilize. Result : Free urea and pure urea hydrolyzed completely in 7 days. Nitrification was complete by the end of threeweeks. The presence of MDU or DMTU had no inhibitory or stimulatory effect on this hydrolysis. The mineralization of MDU proceeded rapidly to completion with only a 2 day lag period at a rate similar to that of urea. The initation of hydrolysis of DMTU was delayed ten days; posibly due to a lack of microbial populations capable of attacking this N product. After this lag period, the majority of the DMTU mineralized in 25 days. In the second soil type, DMTU minearlized 85%in 35 days. Test substance . Test % % % substance Urea MDU DMTU UF6 80.2 12.1 3.7 UF12 60.7 20.1 7.5 UF15 52.3 20.2 8 .3 Pure urea 100 --- --- 

### Conclusion : Only triuret and DMTU components showed any slowrelease character. Since these fractions made up only a small percentage of each material tested the ureaforms probably have limited value as slowrelease sources. Reliability : (2) valid with restrictions Peer reviewed data; no data on GLP 10.07.2007 (2)

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### p. 36



# 4 . Ecotoxicity

4 .1 ACUTE/PROLONGEDTOXICITY TOFISH 4 .2 ACUTE TOXICITY TOAQUATIC INVERTEBRATES 4.3 TOXICITY TO

AQUATIC PLANTS E.G. ALGAE 4.4 TOXICITY TOMICROORGANISMS E.G. BACTERIA 4.5 .1 CHRONIC TOXICITYTO FISH 4.5 .2 CHRONIC TOXICITYTOAQUATIC INVERTEBRATES 4.6 .1 TOXICITY TOSEDIMENT DWELLING ORGANISMS 4.6 .2 TOXICITY TO

TERRESTRIAL PLANTS 4 .6.3 TOXICITY TOSOIL DWELLING ORGANISMS 

### 4.6 .4 TOX . TOOTHER NON MAMM . TERR. SPECIES 4.7 BIOLOGICAL EFFECTS MONITORING 4.8 BIOTRANSFORMATION AND KINETICS Type : other Dog. product . 

### Id 68611-64-3 Date 29.02.2008

Remark : The methylenediurea is hydrolysed and decarboxylated to give an aminated methylurea, which then spontaneously hydrolyses to hydroxymethylurea. The enzyme fromOchrobactrumanthropi also hydrolyses dimethylenetriurea and trimethylenetetraurea as well as ureidoglycolate, which is hydrolysed to urea and glyoxylate, and allantoate, which is hydrolysed to ureidoglycolate, ammonia and carbon dioxide . Reliability : (4) not assignable Original article not reviewed 19 .07.2007 Type : other Deg. product . (1)(8)

Remark : The distinguishing characteristics of methylene urea 23/32- - .r . w . 

## 4 . Ecotoxicity Id 68611-64-3 Date 29.02.2008 products versus all other nitrogen fertilizers is their availability through the action of soil microorganisms. The shorter-chained water-soluble polymers are readily digestible by soil microorganisms and release nitrogen to the soil as ammoniumin a relatively short period of time. The longer-chain polymers contain water-insoluble nitrogen, which is more slowly digested by soil microorganisms. Nitrogen frommethylene urea and ureaformis converted directly back to the ammonium formgradually throughout the growing season. Reliability : (4) not assignable Product data sheet 10 .07.2007 

### 4 .9 ADDITIONAL REMARKS

24/32 

### p. 37

(6)

### p. 38



# 5 . Toxicity

5.0 TOXICOKINETICS, METABOLISM AND DISTRIBUTION 5.1 .1 ACUTE ORAL TOXICITY 5 .1 .2 ACUTE INHALATION TOXICITY 5.1 .3 ACUTE DERMAL TOXICITY 5.1 .4 ACUTE TOXICITY, OTHER ROUTES 5 .2.1 SKIN IRRITATION 5.2 .2 EYE IRRITATION 5.3 SENSITIZATION 5.4 REPEATED DOSE TOXICITY 5.5 GENETICTOXICITY'IN VITRO' 5.6 GENETICTOXICITY'IN VIVO' 5.7 CARCINOGENICITY 5.8 .1 TOXICITY TOFERTILITY 5.8.2 DEVELOPMENTAL TOXICITYITERATOGENICITY 5.8.3 TOXICITY TOREPRODUCTION, OTHER STUDIES 5 .9 SPECIFIC INVESTIGATIONS 

### 5 .10 EXPOSURE EXPERIENCE Id 68611-64-3 Date 29.02.2008

25/32

### p. 39



## 5 . Toxicity 5.11 ADDITIONAL REMARKS Id 68611-64-3 Date 29.02 .2008

26/32

### p. 40



# 6 . Analyt . Meth. for Detection and Identification

6 .1 ANALYTICAL METHODS 6.2 DETECTIONAND IDENTIFICATION Id 68611-64-3 Date 29.02.2008

27/32

### p. 41



## 7. Eff. Against Target Org. and Intended Uses

7.1 FUNCTION 7.2 EFFECTS ON ORGANISMS TOBE CONTROLLED 7.3 ORGANISMS TO BE PROTECTED 7.4 USER 7.5 RESISTANCE Id 68611-64-3 Date 29.02.2008

28/32

### p. 42



## 8. Meas. Nec. to Prot. Man, Animals, Environment

8 .1 METHODS F1A14DLlWG ANDSTOtt1ING 

### 8.2 FIRE GUIDANCE 8.3 EMERGENCY MEASL4 :;NES 8.4 POSSHL OF ,RENDER11CG SU6ST. HMMILESs 8 .5 WASTE MANAGEMENT 

### 8.6 SIDE-EFFECTS DETECTION 8 .7 SUBSTANCE RBMT]BRED AS DANGERetJS FOR_9 

### 8.8 REACTfVfJTY To1VA%RMCEK'fPd"ERAI1TEMA . Id 68611-64-3 Date 29.02.2008

29/32

### p. 43



# 8 . Meas. Nec. to Prot. Man, Animals, Environment

8 .1 METHODS HANDLING ANDSTORING 8 .2 FIRE GUIDANCE 

### 8.3 EMERGENCY MEASURES 8.4 POSSFB. OF RENDERING SUBST~ HARMLESS 8.5 WASTE MANAGEMENT 8.6 SIDE-EFFECTS DETECTION 8.7 SUBSTANCE REGISTEREDAS DANGEROUS- FOR GROUND~WATER 8.8 REACTIVITYTOWARDS CONTAINER MATERIAL Id 68611-64-3 Date 29.02.2008

29/32

### p. 44



## 9 . References Id 68611-64-3 Date 29.02.2008 (1) Can. J . Microbiol . 43 (1997) 1111-1117.

http://www

.orenza.u-psud.fr/query_by_ec.php?EC number--EC%203

. .3.21 (2) Christianson, CB, Carter, MF and Holt, LS (1988)

Mineralization and Nitrifcation of Ureaform Fertilizers. Fertilizer Research, 17: 85-95 

### (3) DeJong and DeJonge (1953) as cited in Kaempffe GC and Lunt

OR (1967) 

### (4) Epiwin v3.20 (5) Hays JT and Haden WW (1966) Soluble fraction of ureaform - nitrification, leaching and burning. J Ag Food Chem Vol 14 No 4pp 339-341 

### (6) http://www .howardfertilizer .com/nugro types.htm (7) Jahns, T and Kaltswasser, H (2000) Mechanism ofMicrobial Degradation of SlowRelease Fertilizers, Journal of Polymers and the Environment V 8 No 1, pp 11-16 (8) Jahns, T., Schepp, R ., Kaltwasser, H. Purification and characterisation of an enzyme froma strain of Ochrobactrum anthropi that degrades condensation products of urea and formaldehyde (ureaform) . (9) Kaempffe GCand Lunt OR (1967) Availability of various

fractions of urea-formaidehyde. J Agr Food ChemV 15 No 6 pp 967-971 

### (10) Katz, SE and Fassbender, CA(1966) Biodegradability of

Ureaformaldehydes and Related Compounds. J Agr and Food Chemistry V 14, No 4 pp 336-339 . (11) Long and Winsor (1960) as cited in Kaempffe and Lunt (1967) (12) MITI database (2002) (http://www .safe.nite.go.jp/english/db.html) Study published 2002/11/8. (13) Murray, T.P., Austin, E.R., Howard, R .G., and Horn R

.C . Anal . Chem

., vol 54, 1505, 1982. 

### (14) The Fertilizer Institute (1983) Formaldehyde Task Group:

Formaldehyde Use in Urea Based Fertilizers (15) The Fertilizer Institute (2007) Personal Communication with

William Herz, VP, Scientific Affairs, TFI, Washington, DC (16) USEPA(1983) 21 C .F .R . § 184.1923 Urea. Title 21 - Food and Drugs (17) USEPA (2002) http://www .epa.gov/fedrgstr (18) USEPA (2002) http://www .epa .gov/oppsrrd1/REDs/urea tred.htm http://216.239.51 .104/search?q=cache:p-1264Z8FFIJ :www .fda.go vcder/ogd/rld/12154s24 .pdf+FDA+category+C+urea&hl=en&ct=clnk &d=1 &gl=us 

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## 9 . References (19) USEPA (no date specified) AP 42, Fifth Edition, and Volume I

Chapter 8: Inorganic Chemical Industry http://www

.epa.gov/ttn/chief/ap42/ch08/final/c08s02.pdf Id 68611-64-3 Date 29.02.2008

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## 10. Summary and Evaluation

10.1 END POINT SUMMARY 

### 10.2 HAZARDSUMMARY 10.3 RISK ASSESSMENT Id 68611-64-3 Date 29.02.2008

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