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 

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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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### UNIVAR USA - MSDS 

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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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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