Why Replace TCE & Chlorinated Solvents? Heidi Wilcox Surface 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 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

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 ? and... YES A GREAT METAL CLEANER??? A FABULOUS VAPOR DEGREASER??? AN EXCELLENT SOLVENT??? and... YES

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 function unconsciousness death 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 1 Chlorinated hydrocarbon* 2 HCFC 3 HFC 4 HFE 5 nPB 6 Volatile Methylsilioxanes 7 Dichloroethylene *Replaced Solvents

Health Comparison Handout

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

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

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

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

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

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!

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 # 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

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??

More In Depth Information with Rich Bizzozero (OTA) 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 – 3:330 7B Everything You Ever Wanted To Know About Surface Cleaning But Were Afraid to Get Your Hands Dirty!

THE END THANK YOU FOR YOUR TIME Now Jason Marshall