1. Why Replace TCE & Chlorinated Solvents?
Heidi Wilcox
Surface Solutions Laboratory (SSL)
Toxics Use Reduction Institute (TURI)
University of Massachusetts Lowell
NEWMOA September 28th, 2005

2. Overview Who we are & what we do TURI & SSL DOES EVERYONE KNOW US ?
Why TCE?
About TCE
Health
Environmental & WE regulations/thresholds
EPA/TURI Grant
Alternatives
Vapor degreasing drop-ins (solvents)
Aqueous
The Database & how SSL can Help!

3. Toxic Use Reduction Institute
The Toxics Use Reduction Institute (TURI) researches, tests and promotes pollution prevention and alternatives to toxic chemicals used in Massachusetts industries and communities
Came out of TUR Act of early 1990’s
Sister agency to OTA
NON REGULATORY!!!!!!

4. The Surface Solutions Lab (SSL)
TURI established the Surface Cleaning Laboratory
Now known as the Surface Solutions Laboratory (SSL)
Designed with the capability to evaluate the effectiveness of different cleaning chemistries and equipment for a variety of substrates and contaminants
The goal is to assist industry in the search for safer cleaning processes
By developing and promoting safer alternatives to hazardous solvents
A special focus on aqueous/semi-aqueous cleaners

5. The Elimination of Solvent Exposure in Surface Cleaning
The focus of SSL is to replace hazardous solvents with a special focus on the halogenated hydrocarbons
30% of trials have been to replace halogenated solvents
30% were conducted to replace other hazardous solvents
Toluene, MEK, N-methyl-2-pyrollidone, etc.
Others were contaminant driven concerns

6. TCE Grant- TURI/OTA EPA
Identify small, non-filing users of TCE (chlorinated solvents). Project is targeted at smaller businesses using chlorinated solvents, who may not have direct access to pollution prevention information & resources
Focus primarily on cleaning
Vapor degreasing, Immersion, Hand wipe & Others
Offer technical assistance to reduce or eliminate chlorinated solvent use
Offer compliance assistance with MACT standards
Disseminate information

7. Why Focus on TCE?
In 2003 the Mass Toxics Use Reductions Program (TURA) initiated a High Priority Substances Strategy (HPS)
It recognized chemicals of greatest concern in the state & aimed to reduce or eliminate them
TCE is on the TURA more Hazardous Substances list
Chemicals on the HPS were chosen based on their potential for negative impacts on human health and the environment & their LEVEL of use in Massachusetts

8. What is TCE ? and... YES A GREAT METAL CLEANER???
A FABULOUS VAPOR DEGREASER???
AN EXCELLENT SOLVENT???
and...
YES

9. It is Also …… A man-made chlorinated solvent = C2HCl3
A potentially dangerous health hazard
Identified as a high priority substance by TURA
Made the list because:
It was determined to be especially TOXIC
It was used in sufficient quantity in MA
Viable alternatives DO exist for most applications

10. Work Environment Problems
Hazardous solvents have been & continue to be used in cleaning applications
These chemicals pose a series of health threats or hazards for exposed workers
There exists a need to control and/or replace/substitute/eliminate such hazards
Control features are not always fool proof
Can lead to worker & environmental exposures that will cost money

11. Other Issues to Consider
Environmental accountability
Increasing regulation on toxic solvents
Disposal costs & other regulations
Community perception
WE ARE HERE TO HELP INDUSTRY THRIVE & PROTECT WORKERS & THE ENVIRONMENT

12. TCE Usage Patterns 80% = Vapor degreasing Fabricated metal parts
Some textiles
5% intermediate product in organic chemicals or pharmaceuticals
5% solvent for dry-cleaning, pre and post spotting and chemical extractor
10% exported
(EPA 2004)

13. Sources of TCE Exposure
Potential Exposure Routes
Breathing vapors at work, near a factory that makes or used TCE, off gassing from consumer products (adhesive, paint etc…)
Ingestion by eating contaminated food
Direct skin contact such as bathing or washing in contaminated water or direct
Drinking contaminated water (wastewater)
Potentially 400,000 U.S. workers exposed annually
(TCE fact sheet Lowell Center 2003)

14. Workplace Exposure Limits
OSHA
PEL = 100 ppm TWA 8-hr wk shift
200 ppm not to be exceeded during any 15 min. work period
300 ppm for 5 minutes in any 2-hour work period
NIOSH
REL = 25 ppm TWA 10-hour work shift
ACGIH
REL =50 ppm TWA 8-hour work shift
100 ppm as STEL (Short Term Exposure Limit)

15. TCE Target Organs Brain – headache, depression, coma
Heart – irregular heartbeat
Liver – acute chemical hepatitis cirrhosis
Kidney – tubular injury
Skin - dermatitis

16. Health Effects of TCE Inhalation Exposure (handout)
Breathing Small Amounts
CNS effects
sleepiness
fatigue
headache
confusion
dizziness
poor coordination
loss of concentration
Other effects
lung & skin irritation
Breathing Large Amounts
May Cause;
impaired heart function
unconsciousness
death
Large amounts for long period of time;
(Chronic exposures)
nerve damage
kidney & liver damage

17. Cirrhosis & Dermatitis

18. TCE Exposure & Cancer Risk
9th Report on Carcinogens by National Toxicology Program (NTP) determined TCE to be an anticipated Carcinogen
International agency for Research on Cancer (IARC) determined TCE to be a probable carcinogen to humans
Animal studies -Liver, Kidney, Lung
Epi. Studies – Kidney, Liver, Cervix, Lymphatic

19. TCE Release Patterns TCE’s major environmental releases are;
AIR - emissions from vapor degreasing
Water - wastewater from metal finishing, paint and ink formation, electronics, textiles electronics component manufacturing and adhesive and rubber industries.

20. Environmental Fate
Volatile & evaporates quickly into air during cleaning operations. Can break down into phosgene, a known lung irritant
Precipitation carries TCE to groundwater. TCE is listed as # 1 groundwater contaminant & is in over 60% of Super Fund sites.
Atmospheric lifetime 1-2 weeks
Persistence in soil & ground water is longer & can have a half life up to 10 months

21. What Participants Asked For
Drop in replacements for TCE in existing vapor degreasing equipment
Easiest for them, less time consuming
Recently spent money on machinery

22. How to Find Drop-in Replacements for TCE?
Literature search
Look at viability
Chemically (VP, FP Surface Tension) (HANDOUT)
Environmentally (ODP, GWP, VOC)
Evaluate health risks (HANDOUT)
Contact Vendors for samples
Test chemistries
Develop testing matrix – soils & substrates
Immersion & Vapor degreasing trials

23. Where there is a Will there is a Way! Our Homemade Vapor Degreaser

24. Identified Drop-In Solvents Alternatives to Chlorinated Solvents
Identified 20 alternative drop-in solvent degreasers
Six Classes of Chemicals
Hydrochlorofluorocarbon
Hydrofluorocarbon
Hydrofluroethers
Bromopropane
Volatile Methylsilioxanes
Dichloroethylene
Class
Base Chemical 1
Chlorinated hydrocarbon* 2
HCFC 3
HFC 4
HFE 5
nPB 6
Volatile Methylsilioxanes 7
Dichloroethylene
*Replaced Solvents

25. Health Comparison Handout

26. Chlorinated Solvents Trichloroethylene (TCE)
ACUTE EFFECTS
(SHORT TERM)
CHRONIC EFFECTS
(LONG TERM)
CANCER HAZARDS
Inhaled, acts as CNS depressive & exposure can cause dizziness, unconsciousness,, nausea & vomiting.
Repeated contact can cause irritation, blistering, roughening and cracking of exposed skin.
It may cause mutations & possible impaired fetal development.
Exposure can result in skin irritation and corneal injury
Repeated exposure can cause memory loss, headache, depression and weakness in the arms and legs.
There is evidence that TCE causes lung kidney & liver cancer in animals.
GI absorption is rapid if ingested and can produce CNS depression & chemical pneumonia
Drinking or ingesting large amounts may cause liver and kidney damage, impaired immune function.
It may cause lung and liver cancer.
Very high levels can cause irregular heartbeat which can be fatal.
Breathing for long periods of time may cause impaired heart function, unconsciousness & death
NTP & IARC anticipated & probable human carcinogen

27. HydroChloroFluoroCarbon AGC Chemicals - AK-225
ACUTE EFFECTS
(SHORT TERM)
CHRONIC EFFECTS
(LONG TERM)
CANCER HAZARDS
Can cause eye and skin irritation and redness
Prolonged inhalation exposure can cause hepatitis, heart irregularities or death
May cause liver cancer
Exposure can cause shortness of breath & confusion
Shows liver enlargement in animal tests ?
High acute exposure can cause unconsciousness, cardiac irregularities and be fatal
3 Rows and much less information know then about TCE

28. 3 Rows and much less information know then about TCE
HydroFluoroCarbon DuPont -Vertrel CCA, MCA, HD Degreaser C, Flux Remover C
ACUTE EFFECTS
(SHORT TERM)
CHRONIC EFFECTS
(LONG TERM)
CANCER HAZARDS
Can cause eye & skin irritation, pain, redness and swelling. May also cause blurred vision
Prolonged inhalation exposure can cause liver & lung damage
Not listed as a carcinogen b IARC, NTP, OSHA or ACGIH
Exposure can cause shortness of breath, confusion, dizziness and weakness
May cause heart muscle damage, chemical pneumonia and pulmonary edema ?
High acute exposure can cause unconsciousness, cardiac irregularities and death
3 Rows and much less information know then about TCE

29. HydroFluoroEther 3M - Novec HFE 7100, 7200 & 71DE
ACUTE EFFECTS
(SHORT TERM)
CHRONIC EFFECTS
(LONG TERM)
CANCER HAZARDS
Can cause eye and skin irritation, swelling, itching, drying and blurred vision
Prolonged exposure could cause cardiac sensitization and CNS depression
No available information
Inhalation exposure can cause respiratory irritation such as cough, running nose, throat pain and headache ?
High acute exposure can cause CNS depression, dizziness, drowsiness, slurred speech, slowed reaction time & unconsciousness
3 Rows and much less information know then about TCE

30. N-Propyl Bromide EnviroTech - Ensolv, Ensolv A; Petroferm – Lenium GS, ES; Kyzen – Metalnox M6960
ACUTE EFFECTS
(SHORT TERM)
CHRONIC EFFECTS
(LONG TERM)
CANCER HAZARDS
Can cause eye and skin irritation and redness
Prolonged exposure may cause lung, liver and kidney damage
No available information
Ingestion of a large amount can cause abdominal pain, nausea and vomiting
Extended skin exposure may lead to pain, cracking and dermatitis ?
High inhalation can cause respiratory tract irritation, CNS depression and anesthetic effects
3 Rows and much less information know then about TCE

31. Issues with Solvent to Solvent Substitutions
Often deemed viable alternative due to less environmental regulations
Does this make them safer for worker?
Are we trading one problem for another?
nPB for TCE recent research ANA in Toronto (handout)
J. Majersik, MD, University of Utah
Severe human neurotoxin but less ODP
Possible interim step NOT a solution!

32. What ARE the BETTER Solutions?
Aqueous Cleaners
Can be used diluted
Possibility of recycling and reuse of cleaner and water
Hopefully eliminates need for air permits due to solvents or hazardous waste disposal permits and the costs associated with both
Reformulate Cleaner – Green Chemistry
Process change
Eliminate contaminant to be cleaned
Eliminate cleaning all together
Change materials to avoid need for cleaning

33. Aqueous & Semi Aqueous Alternatives to TCE

34. SSL Testing on Aqueous Alternatives (handout)
Worked closely with over 20 companies trying to replace TCE in cleaning
A wide range of industries are represented by these companies
Aircraft
Electronics
General Mfr
Metal working
Optical
Plating

35. Summary of Aqueous Alternatives Testing to TCE
21 Vendors
44 Products
11 Product Classes

36. Contaminants Removed Conducted over 100 experiments
11 Contaminant types
Abrasives
Buffing Compounds
Coatings
Fluxes
Grease
Inks
Paints
Cutting Fluids
Lubricants
Oils
Waxes

37. Alternative Cleaner Classifications
# of Products
Alkaline Aqueous 23
Caustic 1
Ester 3
HCFC
Neutral Aqueous 2
Organic
Petroleum Distillate
Semi-Aqueous
Terpene 5
Terpene-Organic
Terpene-Semi-Aqueous

38. Cleaning Varies from Case To Case
Process specific & pilot testing on potential replacement cleaning chemicals is recommended
Vendor information & alternatives database is available on line at

39. SOOOOO………
IF WE CAN FIND A VIABLE ALTERNATIVE…..
WHY NOT DO IT??

40. More In Depth Information with Rich Bizzozero (OTA)
Barriers & Challenges
More In Depth Information
with Rich Bizzozero (OTA)

41. Tools & Resources for TUR
Try it on your own
Talk to others industry
Use supply chain opportunities
Use SSL’s online Simple Solutions Database
Obtain a list of alternatives that are substrate, contaminant and equipment specific
Call & ask SSL/OTA/DEP for Help

42. Questions????? Alternatives Assessment Information call 978 934 3133
Jason Marshall or Heidi Wilcox
*************************************************
Hands-on Solvent Substitution Workshop
Tomorrow 1:30 – 3:330
7B Everything You Ever Wanted To Know About Surface Cleaning But Were Afraid to Get Your Hands Dirty!

43. THE END
THANK YOU FOR YOUR TIME
Now
Jason Marshall