Slide 1 - TURI by jizhen1947


									Toxics Use Reduction Institute

              Why Replace TCE &
             Chlorinated Solvents?

                           Heidi Wilcox
               Surface Solutions Laboratory (SSL)
              Toxics Use Reduction Institute (TURI)
               University of Massachusetts Lowell

              NEWMOA September 28th, 2005
• Who we are & what we do
• 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

        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
  – 30% were conducted to replace other hazardous
    • 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 ?
                It is Also ……
• A man-made chlorinated solvent = C2HCl3

• A potentially dangerous health hazard

• Identified as a high priority substance by
  – 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

           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

 – PEL = 100 ppm TWA 8-hr wk shift
 – 200 ppm not to be exceeded during any 15 min. work
 – 300 ppm for 5 minutes in any 2-hour work period

 – REL = 25 ppm TWA 10-hour work shift

 – 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    Breathing Large
CNS effects                  Amounts
  sleepiness                  May Cause;
  fatigue                    impaired heart function
  headache                   unconsciousness
  confusion                  death
  dizziness                Large amounts for long
  poor coordination          period of time;
  loss of concentration     (Chronic exposures)
Other effects                nerve damage
  lung & skin irritation    kidney & liver damage
Cirrhosis & Dermatitis

      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       Class   Base Chemical
  drop-in solvent degreasers              Chlorinated
                                   1      hydrocarbon*
• Six Classes of Chemicals
                                   2      HCFC
  –   Hydrochlorofluorocarbon
  –   Hydrofluorocarbon            3      HFC
  –   Hydrofluroethers             4      HFE
  –   Bromopropane
                                   5      nPB
  –   Volatile Methylsilioxanes
  –   Dichloroethylene             6      Methylsilioxanes

                                   7      Dichloroethylene
                                       *Replaced Solvents
Health Comparison Handout
                    Chlorinated Solvents
                                Trichloroethylene (TCE)
     ACUTE EFFECTS                     CHRONIC EFFECTS                  CANCER
      (SHORT TERM)                       (LONG TERM)                    HAZARDS
Inhaled, acts as CNS               Repeated contact can cause           It may cause
depressive & exposure can          irritation, blistering, roughening   mutations & possible
cause dizziness,                   and cracking of exposed skin.        impaired fetal
unconsciousness,, nausea &                                              development.
Exposure can result in skin        Repeated exposure can cause          There is evidence
irritation and corneal injury      memory loss, headache,               that TCE causes lung
                                   depression and weakness in           kidney & liver cancer
                                   the arms and legs.                   in animals.
GI absorption is rapid if          Drinking or ingesting large          It may cause lung
ingested and can produce CNS       amounts may cause liver and          and liver cancer.
depression & chemical              kidney damage, impaired
pneumonia                          immune function.
Very high levels can cause         Breathing for long periods of        NTP & IARC
irregular heartbeat which can      time may cause impaired heart        anticipated &
be fatal.                          function, unconsciousness &          probable human
                                   death                                carcinogen
                     AGC Chemicals - AK-225
    ACUTE EFFECTS               CHRONIC EFFECTS               CANCER
     (SHORT TERM)                 (LONG TERM)                 HAZARDS
Can cause eye and skin          Prolonged inhalation      May cause liver cancer
irritation and redness          exposure can cause
                                hepatitis, heart
                                irregularities or death
Exposure can cause shortness    Shows liver enlargement
of breath & confusion           in animal tests
High acute exposure can
cause unconsciousness,
cardiac irregularities and be
                                            ?                      ?
       3 Rows and much less information know then about TCE
           DuPont -Vertrel CCA, MCA, HD Degreaser C, Flux Remover C

    ACUTE EFFECTS                  CHRONIC EFFECTS                  CANCER
     (SHORT TERM)                    (LONG TERM)                    HAZARDS

Can cause eye & skin irritation,   Prolonged inhalation         Not listed as a
pain, redness and swelling.        exposure can cause liver &   carcinogen b IARC,
May also cause blurred vision      lung damage                  NTP, OSHA or ACGIH

Exposure can cause shortness       May cause heart muscle
of breath, confusion, dizziness
and weakness
                                   damage, chemical
                                   pneumonia and pulmonary
High acute exposure can
cause unconsciousness,
cardiac irregularities and death             ?                         ?
             3 Rows and much less information know then about TCE
            3M - Novec HFE 7100, 7200 & 71DE

     ACUTE EFFECTS               CHRONIC EFFECTS                   CANCER
      (SHORT TERM)                 (LONG TERM)                     HAZARDS

Can cause eye and skin           Prolonged exposure could      No available
irritation, swelling, itching,   cause cardiac sensitization   information
drying and blurred vision        and CNS depression

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 &
                                            ?                          ?
             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                   CHRONIC EFFECTS                  CANCER
     (SHORT TERM)                     (LONG TERM)                    HAZARDS

Can cause eye and skin              Prolonged exposure may       No available
irritation and redness              cause lung, liver and        information
                                    kidney damage

Ingestion of a large amount         Extended skin exposure
can cause abdominal pain,
nausea and vomiting
                                    may lead to pain, cracking
                                    and dermatitis                       ?
High inhalation can cause
respiratory tract irritation, CNS
depression and anesthetic
                                               ?                         ?
    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

• 11 Contaminant
                          –   Inks
                          –   Paints
  –   Abrasives
                          –   Cutting Fluids
  –   Buffing Compounds
                          –   Lubricants
  –   Coatings
                          –   Oils
  –   Fluxes
                          –   Waxes
  –   Grease
               Alternative Cleaner
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

• Vendor information & alternatives database
  is available on line at


  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
  – Obtain a list of alternatives that are substrate,
    contaminant and equipment specific

• Call & ask SSL/OTA/DEP for Help
    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

     Jason Marshall

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