Toxics Use Reduction Institute Why Replace TCE & Chlorinated Solvents? Heidi Wilcox Surface Solutions Laboratory (SSL) Toxics Use Reduction Institute (TURI)

Toxics Use Reduction Institute

Why Replace TCE & Chlorinated Solvents?

Heidi WilcoxSurface Solutions Laboratory (SSL)

Toxics Use Reduction Institute (TURI)University of Massachusetts Lowell

NEWMOA September 28th, 2005

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!

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!!!!!!

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

The Elimination of SolventExposure 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

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

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

What is TCE ?• A GREAT METAL CLEANER???

• A FABULOUS VAPOR DEGREASER???

• AN EXCELLENT SOLVENT???

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

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

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

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)

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)

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)

TCE Target Organs

• Brain – headache, depression, coma

• Heart – irregular heartbeat

• Liver – acute chemical hepatitis cirrhosis

• Kidney – tubular injury

• Skin - dermatitis

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 functionunconsciousnessdeath

Large amounts for long period of time;

(Chronic exposures)nerve damage

kidney & liver damage

Cirrhosis & Dermatitis

http://www.osh.dol.govt.nz

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

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.

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

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

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

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

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

1Chlorinated hydrocarbon*

2 HCFC

3 HFC

4 HFE

5 nPB

6Volatile Methylsilioxanes

7 Dichloroethylene

*Replaced Solvents

Health Comparison Handout

Chlorinated SolventsTrichloroethylene (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

HydroChloroFluoroCarbonAGC Chemicals - AK-225



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

HydroFluoroCarbonDuPont -Vertrel CCA, MCA, HD Degreaser C, Flux Remover C



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

HydroFluoroEther3M - Novec HFE 7100, 7200 & 71DE



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


N-Propyl BromideEnviroTech - Ensolv, Ensolv A;

Petroferm – Lenium GS, ES; Kyzen – Metalnox M6960



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


Issues withSolvent 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!

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

Aqueous & Semi Aqueous Alternatives to TCE

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

Summary of Aqueous Alternatives Testing to TCE

• 21 Vendors

• 44 Products

• 11 Product Classes

Contaminants Removed

• Conducted over 100 experiments

• 11 Contaminant types – Abrasives– Buffing Compounds– Coatings– Fluxes– Grease

– Inks– Paints– Cutting Fluids– Lubricants– Oils– Waxes

Alternative Cleaner Classifications

Class # of Products

Alkaline Aqueous 23

Caustic 1

Ester 3

HCFC 1

Neutral Aqueous 2

Organic 1

Petroleum Distillate 3

Semi-Aqueous 2

Terpene 5

Terpene-Organic 1

Terpene-Semi-Aqueous 2

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 www.cleanersolutions.org/SimpleSolutions/

SOOOOO………

IF WE CAN FIND A VIABLE ALTERNATIVE…..

WHY NOT DO IT??

Barriers & Challenges

More In Depth Information

with Rich Bizzozero (OTA)

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

Questions?????

Alternatives Assessment Information call 978 934 3133

Jason Marshall or Heidi Wilcox

*************************************************

Hands-on Solvent Substitution Workshop Tomorrow 1:30 – 3:3307B Everything You Ever Wanted To Know

About Surface Cleaning But Were Afraid to Get Your Hands Dirty!

THE END

THANK YOU FOR YOUR TIMENow

Jason Marshall

Documents

Toxics Use Reduction Institute Why Replace TCE & Chlorinated Solvents? Heidi Wilcox Surface Solutions Laboratory (SSL) Toxics Use Reduction Institute (TURI)