TCE replacement discussion 

Terri Zick to: Christopher Lambesis, Todd Ramaly 

Cc: Jake Gadd, Kathy Wilson 

03/31/2009 03:54 PM 

From: Terri Zick <tzick@cticompanies.com> 

To: Christopher Lambesis/R5/USEPA/US@EPA, Todd Ramaly/R5/USEPA/US@EPA 

Cc: Jake Gadd <jakegadd@owossographic.com>, Kathy Wilson 

<kathywilson@owossographic.com> 

ChristopherAttached, please find the discussion regarding the replacement of TCE as a means of developing plates. 

In addition, the MSDS for the material currently in use is attached for your records. 

Please let me know if there are questions. 

Thank you 

Terri Zick 

313-300-7401 

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UNIVAR USA - MSDS 

V 

univAR 

Univar USA Inc. 

17425 NE Union Hill Road 

Redmond, WA 98052 

(425) 889-3400 

For Emergency Assistance involving chemicals call - CHEMTREC (800) 424-9300 

The Version Date and Number for this MSDS is : 03/07/2007 - #009 

PRODUCT NAME: N-METHYLPYRROLIDONE 

MSDS NUMBER: BZ556994 

DATE ISSUED: 02/01/2007 

SUPERSEDES: 05/23/2006 

ISSUED BY: 009130 

Safety data sheet 

N-Methylpyrrolidone 

1. Substance/preparation and company identification 

24 Hour Emergency Response Information 

CHEMTREC: 1-800-424-9300 

Distributed by: 

Univar USA Inc. 

17425 NE Union Hill Road 

Redmond, WA 98052 

425-889-3400 

Molecular formula: C(5)H(9)NO 

Molecular weight: 99.00 g/mol 

Chemical family: heterocyclic, amines 

Synonyms: NMP TECHNICAL 

2. Composition/information on ingredients 

CAS Number Content (WW) Chemical name 

872-50-4 99.8 % N-Methylpyrrolidone 

60544-40-3 <= 0.4 % Pyrrolidinone, dimethyl3. Hazard identification 

Emergency overview 

NOT FOR COSMETIC USE 

DANGER: COMBUSTIBLE LIQUID. MAY CAUSE EYE, SKIN AND RESPIRATORY TRACT 

IRRITATION. PROLONGED OR REPEATED CONTACT MAY RESULT IN DERMATITIS. 

INGESTION MAY CAUSE GASTRIC DISTUhttp://commerce.univarusa.com/commerce/Uic?action=DisplayProductDocument&produ 

CONTAINS MATERIAL THAT MAY ADVERSELY AFFECT THE DEVELOPING FETUS BASED ON 

Page 1 of 7 

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ANIMAL DATA. 

THIS PRODUCT CONTAINS A CHEMICAL(S) KNOWN TO THE STATE OF CALIFORNIA TO 

CAUSE BIRTH DEFECTS OR OTHER REPRODUCTIVE HARM. 

Use with local exhaust ventilation. 

Wear chemical resistant protective gloves. 

Avoid contact with the skin, eyes and clothing. 

Potential health effects 

Primary routes of exposure 

Routes of entry for solids and liquids include eye and skin contact, 

ingestion and inhalation. Routes of entry for gases include inhalation and 

eye contact. Skin contact may be a route of entry for liquified gases. 

Acute toxicity: 

Information on: n-Methylpyrrolidone 

NMP is moderately toxic by all routes of exposure; however, due to its low 

vapor pressure, dermal exposure represents the primary hazard in most 

settings. Contact with the liquid results in moderate eye irritation and may 

cause temporary corneal clouding. Skin contact results in mild irritation; 

prolonged skin contact may cause redness and dermatitis. Inhalation of the 

vapors of NMP may result in respiratory irritation. Accidental ingestion of 

the liquid causes gastric disturbances and may result in nausea and 

vomiting. 

Irritation: 

Information on: n-Methylpyrrolidone 

Contact with the liquid can result in irritation. Skin contact should be 

avoided. Prolonged skin contact may result in redness and dermatitis. 

Repeated dose toxicity: 

Information on: n-Methylpyrrolidone 

In animal studies NMP was embryotoxic by the oral, dermal and 

intraperitoneal routes, but only after repeated high doses that approached 

the LD50 or were maternally toxic. Embryotoxicity without maternal toxicity 

was observed at a high concentration in one rat inhalation study, but not in 

others. Testicular effects in rats were noted after repeated, high-dose oral 

and inhalation exposures. NMP was not carcinogenic in rats receiving 

lifetime exposures via inhalation (100 ppm) or the diet. This product 

contains a chemical known to the state of California to cause birth defects 

or other reproductive harm. In a mouse cancer study, high doses of NMP 

produced liver carcinomas & adenomas in males (1089 mg/kg) and liver 

adenomas in females (1399 mg/kg). Middle doses caused liver hypertrophy in 

males (173 mg/kg) but not females (221 mg/kg). No effects were noted at low 

doses in either males (89 mg/kg) or females (115 mg/kg). 

Medical conditions aggravated by overexposure: 

Data available do not indicate that there are medical conditions that are 

generally recognized as being aggravated by exposure to this 

substance/product. 

See MSDS section 11 - Toxicological information. 

4. First-aid measures 

General advice: 

Remove contaminated clothing. 

If inhaled: 

Remove the affected individual into fresh air and keep the person calm. 

Assist in breathing if necessary. Immediate medical attention required. 

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UNIVAR USA - MSDS Page 3 of 7 

If on skin: 

Wash affected areas thoroughly with soap and water. If irritation develops, 

seek medical attention. 

If in eyes: 

In case of contact with the eyes, rinse immediately for at least 15 minutes 

with plenty of water. Seek medical attention. 

If swallowed: 

Rinse mouth and then drink plenty of water. Induce vomiting. Never induce 

vomiting or give anything by mouth if the victim is unconscious or having 

convulsions. Immediate medical attention required. 

5. Fire-fighting measures 

Flash point: 196 deg F (ASTM D93) 

Autoignition: 245 deg C (DIN 51794) 

Lower explosion limit: 1.3 %(V) 

Upper explosion limit: 9.5 cis (V) 

Suitable extinguishing media: 

water spray, dry extinguishing media, foam, carbon dioxide 

Hazards during fire-fighting: nitrous gases 

Protective equipment for fire-fighting: 

Firefighters should be equipped with self-contained breathing apparatus and 

turn-out gear. 

Further information: 

Collect contaminated extinguishing water separately, do not allow to reach 

sewage or effluent systems. 

NFPA Hazard codes: 

Health : 2 Fire: 2 Reactivity: 0 Special: 

6. Accidental release measures 

Personal precautions: 

Wear appropriate respiratory protection. Use personal protective clothing. 

Ensure adequate ventilation. 

Environmental precautions: 

This product is not regulated by RCRA. This product is not regulated by 

CERCLA (Superfund). 

Cleanup: 

Spills should be contained, solidified, and placed in suitable containers 

for disposal. 

For small amounts: Pick up with absorbent material (e.g. sand, sawdust, 

general-purpose binder). Dispose of absorbed material in accordance with 

regulations. 

For large amounts: Pump off product. 

7. Handling and storage 

Handling 

General advice: 

Ensure thorough ventilation of stores and work areas. 

Avoid contact with skin and eyes. Wear suitable gloves and eye/face 

protection. 

Protection against fire and explosion: The product is combustible. 

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Storage 

General advice: 

Containers should be stored tightly sealed in a dry place. 

Storage stability: 

Storage duration: 24 Months 

8. Exposure controls and personal protection 

Advice on system design: 

Provide local exhaust ventilation to maintain recommended P.E.L. 

Personal protective equipment 

Respiratory protection: 

Wear a NIOSH-certified (or equivalent) organic vapour respirator. Observe 

OSHA regulations for respirator use (29 CFR 1910.134). 

Hand protection: 

Wear chemical resistant protective gloves., butyl rubber (butyl) - 0.7 mm 

coating thickness, Consult with glove manufacturer for testing data. 

Eye protection: 

Wear face shield or tightly fitting safety goggles (chemical goggles) if 

splashing hazard exists. Safety glasses with side-shields. 

Body protection: 

Body protection must be chosen depending on activity and possible exposure, 

e.g. head protection, apron, protective boots, chemical-protection suit. 

General safety and hygiene measures: 

Handle in accordance with good industrial hygiene and safety practice. 

Wearing of closed work clothing is required additionally to the stated 

personal protection equipment. Eye wash fountains and safety showers must be 

easily accessible. Wear protective clothing as necessary to minimize 

contact. Wash soiled clothing immediately. When using do not eat or drink. 

When using do not smoke. Gloves must be inspected regularly and prior to 

each use. Replace if necessary (e.g. pinhole leaks). Handle in accordance 

with good industrial hygiene and safety practice. 

9. Physical and chemical properties 

Form: liquid 

Odour: mild, amine-like 

Colour: clear colourless 

pH value: 8.5 - 10 ( 100 g/1, 20 deg C) 

Melting point: -23.6 deg C ( 760 mmHg) 

Boiling point: 204.3 deg C ( 760 mmHg) 

Vapour pressure: 0.32 mbar ( 20 deg C) 

Density: 1.028 g/cm3 ( 25 deg C) (DIN 51757) 

Partitioning coefficient n- -0.46 

octanol/water (log Pow): 

Viscosity, dynamic: 1.796 mPa.s ( 20 deg C) 

Solubility in water: miscible 

Solubility (qualitative): miscible 

solvent(s): organic solvents, 

10. Stability and reactivity 

Substances to avoid: 

strong acids, oxidizing agents 

Hazardous reactions: 

Exothermic reaction. 

Reacts with oxidizing agents. 

Decomposition products: 

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Hazardous decomposition products: carbon monoxide, carbon dioxide, nitrogen 

oxides 

Thermal decomposition: approx. > 300 deg C 

Corrosion to metals: 

No corrosive effect on metal. 

11. Toxicological information 

Acute toxicity 

Oral: 

LD50/mouse: 5,270 mg/kg Slightly toxic. 

Inhalation: 

LC50/rat: > 5.1 mg/l / 4 h 

Inhalation-risk test (IRT): No mortality within 8 hours as shown in animal 

studies. The inhalation of a highly saturated vapor-air mixture represents 

no acute hazard. 

Dermal: 

LD50/rabbit: 4,000 - 8,000 mg/kg Moderately toxic. 

Eye irritation : 

rabbit: Irritant. (BASF-Test) 

Sensitization: 

Skin sensitizing effects were not observed in animal studies. Literature 

data. 

Chronic toxicity 

Repeated dose toxicity: 

Genetic toxicity: 

In the majority of studies performed with microorganisms and in mammalian 

cell culture, a mutagenic effect was not found. A mutagenic effect was also 

not observed in in vivo tests. 

Carcinogenicity: 

Results from a number of long-term carcinogenity studies and short-term 

tests are available. Taking into account all of the information, there is no 

indication that the substance itself is carcinogenic. 

Reproductive toxicity: 

The results of animal studies gave no indication of a fertility impairing 

effect. 

Developmental toxicity/teratogenicity: 

Indications of a developmental toxic / teratogenic effect were seen in 

animal studies. 

12. Ecological information 

Environmental fate and transport 

Biodegradation: 

Test method: OECD 301 E/92/69/EEC, C.4-B 

Method of analysis: DOC reduction 

Degree of elimination: > 90 % 

Evaluation: Readily biodegradable. 

Chemical oxygen demand (COD): 1,600 mg/l 

Biochemical oxygen demand (BOD): Incubation period 5 d: < 2 mg/g 

Absorbable organically-bound halogen (AOX): 

This product contains no organically-bound halogen. 

Environmental toxicity 

Acute and prolonged toxicity to fish: golden orfe/LC50 (96 h): > 500 mg/I 

Acute toxicity to aquatic invertebrates: Daphnia magna/EC5O (24 h): > 1,000 mg/ 

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UNIVAR USA - MSDS Page 6 of 7 

1 

Toxicity to aquatic plants: 

green algae/EC50 (72 h): > 500 mg/1 

Toxicity to microorganisms: 

OECD Guideline 209 bacterium/EC20 (30 min): > 600 mg/1 

Inhibition of degradation activity in activated sludge is not to be 

anticipated during correct introduction of low concentrations. 

13. Disposal considerations 

Waste disposal of substance: 

Incinerate in a licensed facility. 

Do not discharge substance/product into sewer system. 

Container disposal: 

Dispose of in a licensed facility. Recommend crushing, puncturing or other 

means to prevent unauthorized use of used containers. 

14. Transport information 

Land transport USDOT 

Classified as combustible liquid in containers greater than 119 gallons. 

Sea transport IMDG 

Not classified as a dangerous good under transport regulations 

Air transport IATA/ICAO 

Not classified as a dangerous good under transport regulations 

15. Regulatory information 

Federal Regulations 

Registration status: 

TSCA, US released / listed 

Unspecified 

OSHA hazard category: Skin and/or eye irritant, Combustible Liquid, Chronic 

target organ effects reported 

CERCLA RQ CAS Number 

100 LBS 74-89-5 

Chemical name 

methylamine 

State regulations State RTK 

CAS Number Chemical name State RTK 

872-50-4 N-Methylpyrrolidone MA, PA 

CA Prop. 65: 

THIS PRODUCT CONTAINS A CHEMICAL(S) KNOWN TO THE STATE OF CALIFORNIA TO 

CAUSE CANCER AND BIRTH DEFECTS OR OTHER REPRODUCTIVE HARM. 

16. Other information 

HMIS III rating 

Health: 2 Flammability: 2 Physical hazard: 0 

HMIS uses a numbering scale ranging from 0 to 4 to indicate the degree of 

hazard. A value of zero means that the substance possesses essentially no 

hazard; a rating of four indicates high hazard. 

For Additional Information: 

Contact: MSDS Coordinator - Univar USA 

During business hours, Pacific Time - (425) 889-3400 

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UNIVAR USA - MSDS Page 7 of 7 

NOTICE 

Univar USA expressly disclaims all express or implied warranties of merchantibility and fitness 

for a particular purpose with respect to the product or information provided herein, and shall 

under no circumstances be liable for incidental or consequential damages. 

Do not use ingredient information and/or ingredient percentages in this MSDS as a product 

specification. For product specification information refer to a Product Specification Sheet and/or 

a Certificate of Analysis. These can be obtained from your local Univar USA Sales Office. 

All information appearing herein is based upon data obtained from the manufacturer and/or 

recognized technical sources. While the information is believed to be accurate, Univar USA 

makes no representations as to its accuracy or sufficiency. Conditions of use are beyond Univar 

USA's control. Therefore, users are responsible to verify this data under their own operating 

conditions to determine whether the product is suitable for their particular purposes, and they 

assume all risks of their use, handling, and disposal of the product or from the publication or use 

of, or reliance upon, information contained herein. This information relates only to the product 

designated herein and does not relate to its use in combination with any other material or in any 

other process. 

END OF MSDS 

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March 31, 2009 

Mr. Christopher Lambesis 

Environmental Protection. Agency 

Region 5 

77 West Jackson Blvd. 

Mail Code LR-8J 

Chicago.. IL, 60604-3590 

Re: Discussion of TCE Replacement with Alternate Solution; 

Owosso Graphic Arts, Owosso, MI 

Dear Mr. Lambesis, 

At the time of the initial submittal of the petition to delist the wastewater treatment sludge 

generated at Owosso Graphic Arts (OGA), the process generating the sludge included a cleaning 

step prior to etching that was conducted using Trichloroethylene (TCE). As part of OGA's 

demonstrated history of environmental stewardship, its staff has actively sought lower toxicity 

alternatives to numerous process chemicals over the years. Replacement of TCE with an aqueous 

product had been considered even prior to the original petition, however, trials of alternatives 

available at the time failed to meet their strict quality expectations. 

In November, 2007, Owosso conducted trials using an aqueous product designed to replace TCE 

in the process, and shortly thereafter began the transition to the aqueous based material. By 

December 20, 2007 the transition was complete and the remaining TCE was removed from the 

site for disposal. Since that time, the process has further evolved based on performance of the 

aqueous developer. Over time, the aqueous material did not yield the results that OGA required 

for long-term use of the material and they selected an alternate developer (n-methyl-pyrrolidone) 

and implemented a new process which is currently in use. 

Magnesium plates which are to be etched in the system are developed using the material 

described in the attached Material Safety Data Sheet (MSDS). Once the developer has reacted 

with the coating on the top of the magnesium sheet, it is washed in sinks which are directly 

connected to the sanitary sewer. The plates are further heated over an open flameuntil the coating 

is set prior to being placed in one of the etching machines. Residue from the developing process 

is not expected to remain on the sheets after washing and heating, and the development process 

occurs without any direct connection to the etching process (ie. no piping or other mechanical 

means of transferring developer to the etching system exists). 

In the letter to the EPA. dated 1/24/08, Owosso graphic Arts staff also confirmed that the 

remaining unused and spent TCE had been removed from the premises. A copy of the waste 

manifest documenting the removal of the remaining material was provided as an attachment to 

that letter detailing the removal of the chlorinated solvent from the site. While not specifically 

stated in the 1/24/08 letter, it should be noted that the tank and piping previously used in the TCE 

Civil, Geotechnical, Environmental & Construction Materials Engineers 

www,cticompanies.com 
degreasing process was also removed from the premises. No functional means of using . TCE for 

this purpose remains at the facility. While some residual TCE has been detected in the system (as 

discussed in our 1/24/08 letter) since termination of its use, no TCE has been introduced to the 

system since December 20, 2007. 

Should you have additional questions, please do not hesitate to contact me at 313.300-7401. 

Sincerely 

CU and Associates, Inc. 

Tern Zick 

Director of Compliance Services 

Cc: Kathy Wilson 

Jake Gadd