Recognizing, Evaluating, and Controlling Chemical Hazards to
Reduce Occupational Exposure to Hazardous Waste in Academic
Laboratories By: Steve Rupkey, CIH Safety/QA Manager Argonne
National Laboratory
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2 AGENDA Background Anticipation & Recognition Evaluation
Control Disclaimer Take A Way Overview of IH Responsibility
Disclaimer Take A Way Overview of IH Responsibility Toxicology
Health Effects Routs of Entry Exposure Limits Characteristics
Toxicology Health Effects Routs of Entry Exposure Limits
Characteristics Qualitative Quantitative Qualitative Quantitative
Elimination Engineering Administrative PPE Elimination Engineering
Administrative PPE
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Physical & Health Hazards Electrical Safety Noise Radiation
Ergonomics Emergency Response For informational purposes only. Your
Site ESH professional is your best resource! 3 DISCLAIMER Ye Olde
Disclaimer Not covering every IH concept or all hazard types,
e.g.
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Apply industrial hygiene concepts 4 ANTICIPATION RECOGNITION
EVALUATION CONTROL TAKE A WAY Predict your exposure to airborne
hazardous waste
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5 ANTICIPATION RECOGNITION EVALUATION CONTROL INDUSTRIAL
HYGIENE Four Fundamental Elements
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6 ANTICIPATION RECOGNITION EVALUATION CONTROL
Anticipation/recognition of potential or actual hazards
cradle-to-grave concept (research through waste disposal)
INDUSTRIAL HYGIENE Anticipation Proactive
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7 ANTICIPATION RECOGNITION EVALUATION CONTROL
Anticipation/recognition of potential or actual hazards through
knowledge of: Draws upon your knowledge of Materials Operations
Processes Conditions INDUSTRIAL HYGIENE Recognition Judgment of
Exposure Potential
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8 ANTICIPATION RECOGNITION EVALUATION CONTROL Evaluation of the
level of risk: Measurement of exposure intensity Determination of
exposure frequency, and duration Comparison with regulatory,
professional, and internal standards Judgment: weigh all factors
INDUSTRIAL HYGIENE Evaluation Stressor and
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9 ANTICIPATION RECOGNITION EVALUATION CONTROL Methods to
eliminate or reduce exposure Elimination / Substitution Engineering
Controls Administrative Controls PPE Control Prevention INDUSTRIAL
HYGIENE
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Need to understand Toxicity Physical and Chemical properties
Manner and quantity handled These factors help determine: How much
enters the body Route of entry into the body Frequency of exposure
Duration of exposure 10 INDUSTRIAL HYGIENE Estimating Risk of
Exposures
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11 Researchers, HSE personnel and contractors are the frontline
persons responsible for meeting this goal. Examples of HSE programs
that are critical to meeting this goal: RCRA Marking, Handling and
Storage DOT Shipping Hazardous Materials OSHA 1910.120(q) Emergency
Response Chemical Hygiene Plan Waste handling Hazard Communication
Understanding the hazards Personal Protective Equipment Last line
of protection RESPONSIBILITY Teamwork keeps everyone safe and
healthy
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12 You need an understanding of.... ANTICIPATION / RECOGNITIION
Toxicology / Health Effects How material effects the body Routs of
Entry How it enters the body Exposure Limits - How much is allowed
Physical Properties of Chemicals How will it behave
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13 TOXICOLOGY Dose Makes The Poison Paracelsus (1493- 1541) All
chemicals are poisons, there are none that are not. The difference
between a cure and a poison is the dose
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14 TOXICOLOGY Exposure VS. Absorbed Dose Environmental
Stressors EXPOSURE Intensity Frequency Duration Routes of Entry
DOSE Bioavailability Genetics Susceptibility Exposure - substance
available for potential contact with the body Absorbed Dose -
amount of substance that contacts the body and is available to
cause a reaction Absorbed Dose
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15 Degree to which a substance can harm an exposed organism.
Potential for a substance to cause harm (toxicity + dose)
Measurement or estimate of hazard TOXICOLOGY Toxicity VS. Hazard
VS. Risk Toxicity Hazard Risk
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Whats more toxic Mercury vapors Sodium chloride (table salt)
Whats more hazardous? Putting a thermometer in your mouth Ingesting
2 pounds of sodium chloride Whats more risky? It depends 16
TOXICOLOGY What more toxic, hazardous and riskier?
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TOXICOLOGY Dose-Response Relationship Dose (mg/kg body weight)
Response (Percent) 100 50 0 NOEL LOEL 0 5 10 15 20 25 30 35 40 45
NOEL = Highest data point at which there was not an observed affect
of interest LOEL = Lowest data point at which there was an observed
affect of interest LD 50
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Dose Rate of generation Physical state Temperature Genetics
Site of contact with body General health of individual 18
TOXICOLOGY Response depends on many factors
Carcinogens - Induce cancer or increase its incidence Benzene
(Carcinogen 1A) * Reproductive Effects sexual function and
fertility and development of the offspring Karl-Fisher reagent
(Reproductive toxicity 1B) * Mutagens - Inheritable genetic
changes, may effect your offspring or their offspring Benzene
(Mutagen 1B) * 22 Low concentration, long-term exposures CHRONIC
EFFECTS 2012 HazCom Terms *Source: Sigma Aldrich
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Skin Sensitizers - allergic response Respiratory Sensitizers -
hypersensitivity of the airways Specific target organ toxicity -
single exposure, (STOT-SE) means specific, non- lethal target organ
toxicity. Specific target organ toxicity - repeated exposure
(STOT-RE) means specific target organ toxicity 23 Tweeners (my
term) ACUTE - CHRONIC EFFECTS
Occupational Routes of Entry Inhalation Skin contact/skin
absorption Ingestion Injection 25 Contact with the body ROUTES OF
ENTRY
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26 INHALATION Respiratory system Largest surface area Once
inhaled, chemicals are either exhaled or deposited in the
respiratory tract. If deposited, damage can occur through direct
contact with tissue or the chemical may diffuse into the blood
through the lung-blood interface. Upon contact with tissue in the
upper respiratory tract or lungs, chemicals may cause health
effects ranging from simple irritation to severe tissue
destruction. Substances absorbed into the blood are circulated and
distributed to organs that have an affinity for that particular
chemical. Health effects can then occur in the organs, which are
sensitive to the toxicant.
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27 SKIN CONTACT / ABSORPTION Largest organ in the body 2 m 2
Skin contact can cause health effects ranging from relatively
innocuous (redness or mild dermatitis) to more severe destruction
of skin tissue. Many chemicals can also cross the skin barrier and
be absorbed into the blood system. Once absorbed, they may produce
systemic damage to internal organs The eyes are particularly
sensitive to chemicals. Even a short exposure can cause severe
effects to the eyes or the substance can be absorbed through the
eyes and be transported to other parts of the body causing harmful
effects.
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28 Typically an inadvertent exposure route INGESTION Can
swallow via mucus from respiratory system Chemicals that are
insoluble in the fluids of the gastrointestinal tract (stomach,
small, and large intestines) are generally excreted. Others that
are soluble are absorbed through the lining of the gastrointestinal
tract. They are then transported by the blood to internal organs
where they can cause damage.
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Substances may enter the body if the skin is penetrated or
punctured by contaminated objects. Effects can then occur as the
substance is circulated in the blood and deposited in the target
organs. 29 INJECTION Sub cutaneous
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Metabolized - Transformed via chemical reactions in the body
Stored in specific organs - Storage may reduce metabolism and
therefore, increase the persistence of the chemicals in the body.
Excreted - The various excretory mechanisms (exhaled breath,
perspiration, urine, feces, or detoxification) rid the body, over a
period of time, of the chemical. For some chemicals elimination may
be a matter of days or months; for others, the elimination rate is
so low that they may persist in the body for a lifetime and cause
deleterious effects. 30 FATE Metabolism, storage, and
excretion
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31 The concentration to which nearly all healthy workers may be
repeatedly exposed, day after day, without adverse health effects.
Established for many, not all EXPOSURE LIMITS
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32 NOT a relative index of toxicity NOT a fine line between
healthy and unhealthy NOT protective of all workers Limitations
EXPOSURE LIMITS HealthyUnhealthy Above Below
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Noise Heat Stress Cold Stress Vibrations Ionizing Radiation
Non-Ionizing Radiation 33 EXPOSURE LIMITS Also for physical
hazards
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34 Gases / Vapors (ppm) parts per million Particulates /
Aerosols (mg/m 3 ) milligrams per cubic meter Fibers (f/cc) fibers
per cubic centimeter EXPOSURE LIMITS General units of substance
allowed in air
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A ppm is: 1/16 of an inch in a mile 1 penny in $10,000 1 minute
in two years 1 dime in a one-mile-high stack of pennies A ppb is:
One drop of ink in the largest tanker trucks used to haul gasoline
35 EXPOSURE LIMITS A little perspective
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36 Permissible Exposure Limits (PEL) The Law Threshold Limit
Values (TLV) Volunteer (best practice) Recommended Exposure Limits
(REL) - Volunteer EXPOSURE LIMITS Primary organization who sets
OELs
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37 EXPOSURE LIMITS Different types of OELs Ceiling Limits (C)
15 - minutes Short-Term Exposure Limits (STEL) 15-minutes
Time-Weighted- Average (TWA) 8 - hour workday Peak 10-minutes
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38 EXPOSURE LIMITS Exposures are average concentrations over
time sampled 8hr TWA 100 ppm STEL 150 ppm Ceiling 200 ppm Zero ppm
0 1 2 3 4 5 6 7 8 HOURS Peak 500 ppm
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There can be a significant exposure due to skin, eye, or mucous
membrane contact with the vapors, liquids or solids or by direct
contact. Ability to cause irritation, dermatitis, or sensitization
is not considered relevant. Excludes irritant or corrosive effects
in the absence of systemic toxicity EXPOSURE LIMITS Skin (S)
notation - TLV benzene methanol methyl mercury phenol furfural
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40 An acute respiratory exposure: Poses an immediate threat to
loss of life, immediate or delayed irreversible adverse effects on
health Acute eye exposure that would prevent escape from a
hazardous atmosphere EXPOSURE LIMITS Immediately Dangerous to Life
and Health (IDLH)
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41 EXPOSURE LIMITS You should try to understand why the OEL was
set NOT a relative index of toxicity Best Resource: ACGIHs
Documentation of the Threshold Limit Values for Chemical Substances
and Physical Agents & Biological Exposure Indices
OELSubstanceTo PreventAgency 10 ppmAcetic acidAcute irritationOSHA
50 ppmCarbon monoxideStress on cardiovascular systemOSHA 200
ppmAcetaldehydeEye irritationOSHA 1000 ppmAcetoneCNS
(dizziness)OSHA
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Knowledge of the physical state of matter can help anticipate
its movement in the air near your Breathing Zone. 42
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43 PHYSICAL PROPERTIES Physical States of Matter
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SOLIDS Dust and Particulates C44 Dusts Particles from
mechanical grinding or crushing Dusts Particles from mechanical
grinding or crushing Particulates Fine solid or liquid particles
Dust (0.1 30 m) Mists (0.01 10 m) Aerosols (0.01 10 m) Fumes Smoke
Particulates Fine solid or liquid particles Dust (0.1 30 m) Mists
(0.01 10 m) Aerosols (0.01 10 m) Fumes Smoke Powder Granular
Fibers
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45 SOLIDS Dust and Particulates Can: Behave like gases Stay
airborne for long periods Easily be inhaled Form explosive mixtures
Be toxic and corrosive Be combustible and flammable Slough off
material when handled Have a large combined surface area
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LIQUIDS C46 Viscosity The state of being thick, sticky, and
semifluid in consistency, due to internal friction. Viscosity The
state of being thick, sticky, and semifluid in consistency, due to
internal friction. Low Viscosity Acetone Milk Water High Viscosity
Oil Gelatinous Paste Low Viscosity Acetone Milk Water High
Viscosity Oil Gelatinous Paste
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47 Can: Be toxic and corrosive Be absorbed through the skin and
mucus membranes Cause contact related health effects Liquids flow
LIQUIDS
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48 VAPORS Can: Be absorbed through the skin and mucus membranes
Cause contact related health effects Form in the head space Form
when chemicals mix Evaporate to form toxic, corrosive and/or
flammable vapors! Evaporation affected by: Air Speed Temperatures
Relative Humidity Form from solids and liquids Dont confuse vapors
with fumes
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49 GASES Can: Can be toxic and/or corrosive Flammable or
cryogenic Can be lighter than air Can be heavier than air Fill the
space in which it is generated
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50 VAPOR PRESSURE Usually expressed mm Hg The higher the vapor
pressure, the greater the tendency of the substance to evaporate
Tendency to evaporate and become a gas Directly related to temp.
ChemicalVP mm HgTemperature (F) Ethylene Glycol468 Water1868
Acetaldehyde74068 Nitrous oxide4245377
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51 GAS & VAPOR DENSITY Lighter than air (< 1) Will tend
to rise Air (1) (MW = 30) Heavier than air (> 1) Will tend to
sink Can be lighter, heavier, or same density as air (air = 1) VD
of gasoline = 3 4 Where would you expect the vapors to accumulate?
Ventilation plays a role
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52 COMPATIBILITY Can be a good or bad characteristic When
chemicals can remain in contact indefinitely without reaction, they
are compatible. May not always produce a hazard.
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Flammable vapors Hazardous energies Toxic vapors 53 Can
generate and release INCOMPATIBILE Sodium hypochlorite Sodium
hypochlorite Ammonia Always know the compatibility before combining
substances cameochemicals.noaa.gov/reactivity
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54 Health Effects Toxicology How Chemicals Behave Chemical
Compatibility Chemical Compatibility Exposure Routes Exposure
Limits Summary ANTICIPATION / RECOGNITIION
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Based on your of knowledge: How stressors might behave Now they
may interact with your body 55 Evaluate your potential exposure
EVALUATION
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56 Properties of chemicals Work practices and control methods
EVALUATION Thought Exercise - Combine your knowledge Exposure
Assessment Qualitative vs. Quantitative Exposure Assessment
Qualitative vs. Quantitative My educated judgment gives me an
approximate exposure The monitoring results give me an actual
exposures
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RECOGNITION 57 Judgment on whether a worker will be exposed
over the OEL or conservatively, the OEL (action level) EVALUATION
(Qualitative) Qualitative Exposure Assessment
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Risk is the chance or possibility of an adverse outcome You
need to evaluate the risks to assess if your are potentially
exposed to an environmental stressor over an occupational
overexposure limit 58 Assessing your risk of airborne exposure
EVALUATION (Qualitative)
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59 Environmental Stressor Properties must be weighed against
the Risks Factors EVALUATION (Qualitative) Airborne Exposure
Assessment
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RECOGNITION Ask yourself: Is there an OEL? OSHA ACGIH NIOSH
AIHA Do you know why the limit was set? 60 EVALUATION (Qualitative)
Stressor Properties EXPOSURE LIMIT 100 ppm
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RECOGNITION Ask yourself: What type of limit? Combination
Different concentrations 61 EVALUATION (Qualitative) Stressor
Properties 8 Hr TWA 15 Min STEL 10 Min Ceiling
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RECOGNITION Ask yourself: Does the substance emit vapors? Does
it evaporate quickly? Is it a fine powder? Will it pour quickly? Is
there a reaction by-product? It the mixture more toxic? Can I smell
it? Is there an odor threshold? 62 EVALUATION (Qualitative)
Stressor Properties
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Odor vs. toxicity benzene sweet and carcinogen skunk brutal and
irritant Olfactory fatigue hydrogen sulfide now you smell it now
you dont Warning properties mercaptans added to natural gas to give
the characteristic odor carbon monoxide no odor 63 There are times
that you can smell odors at concentrations many times lower than an
exposure limit.
RECOGNITION No OELs, ask: Fire, explosion and/or corrosion
risks Potential for environmental contamination Slip, trips, falls
Ergonomics Heat stress Cryogenics Cuts 65 EVALUATION (Qualitative)
Stressor Properties Other safety hazards?
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Ask yourself: Whether you may be exposed over the OEL using
Risk Factors as a guideline 66 EVALUATION (Qualitative) Stressor
Properties
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67 Ask yourself questions like: How much chemical will be
handled? How long will I be exposed? Will the type of work
performed generate airborne chemicals? Will the work involve
exposure to physical agents? Is there adequate ventilation? Will
the chemicals be handled outdoors vs. indoors? Has their been an
overexpose in the past? EVALUATION (Qualitative) Risk Factors
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68 How much chemical will I handled? Total amount, surface
area, etc. The larger the surface area the more vapors are
evaporated Quantity must be balanced against hazardous nature of
the material However: small quantities of highly toxic or reactive
substances can create significant risk EVALUATION (Qualitative)
Risk Factors
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69 How long will I be exposed? The shorter the work process the
less exposure duration However: a short amount of exposure to a
highly toxic or reactive substance can create significant risk.
EVALUATION (Qualitative) Risk Factors
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Will the type of work performed generate a release? 70 Pouring
Mixing mixing Transferring What if I break a container Outdoors Hot
& sunny vs. cold & cloudy EVALUATION (Qualitative) Risk
Factors
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1-2 minutes per bottle 71 EVALUATION (Qualitative) Example
Consolidating HPLC Waste Potential Contaminants
VentilationTaskExposure Duration Bottles / Day VPOELsWhy OEL?
Methanol (40%) GeneralPour from collection container into 55 gal
drum 1-2 minutes per bottle 4127.2 mm Hg (77) 200 ppm TWA 250 ppm
STEL Skin Eye Irr. Headache s Acetonitrile (59%) GeneralPour from
collection container into 55 gal drum 1-2 minutes per bottle 491.1
mm Hg (77) 20 ppm Skin Systemic effects Various Analytes (1%)
GeneralPour from collection container into 55 gal drum 1-2 minutes
per bottle 4Various What else would you ask?
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Is there adequate ventilation? Local Exhaust Ventilation (LEV)
Can remove airborne agent at the generation source and greatly
reduce the airborne concentration General Ventilation Less
effective than LEV Can reduce airborne concentration by dilution 72
EVALUATION (Qualitative) Risk Factors
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History of personnel being overexposed during this work task?
Look at OSHA Logs Ask site ESH personnel Ask workers about past
projects with air sampling 73 EVALUATION (Qualitative) Risk Factors
Is there a specific OSHA Regulation where you assume overexposure
until proven otherwise? Lead Asbestos Hexavalent Chromium
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Identify sign & symptoms of exposure. If you experience any
of the listed signs and symptoms of overexposure then you may be
overexposed. 74 EVALUATION (Qualitative) Symptoms of Exposure
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75 IRRITATION / BURNING TO NOSE & LUNGS FEEL DIZZY / LIGHT
HEADED / NAUSEA SKIN / RESPIRATORY SENSITIZATION RASH LACRAMATION
HEADACHE COUGHING EVALUATION (Qualitative) Common Acute Health
Effects NAUESA SKIN IRRITANT
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76 Understand all or ask for review by and IH: What are the
waste characteristics? At what concentrations? Does the waste have
an exposure limits? How will the waste be handled? What are the
hazards of the material? What types of controls are in place? What
happens if I spill the material? Waste streams and work procedures
should be reviewed prior to handling EVALUATION (Qualitative)
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77 Your educated and experienced judgment will help you to:
Determine if an exposure over an OEL is likely If air sampling is
required If controls are necessary EVALUATION (Qualitative)
Summary
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EVALUATION (Quantitative) 78 Quantitative Exposure Assessment
Measurement of the stressor for comparison to OELs Must be
conducted by an experienced Industrial Hygienist
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79 Before collecting samples Determine the stressor What OEL(s)
will I use What laboratory will I use Sampling & calibration
equipment Sampling strategy EVALUATION (Quantitative) Examples of
things to consider After collecting samples How to interpret the
results Determine recommendations for corrective actions based on
results Document the monitoring results Inform the employee
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80 Maximum Risk vs. All Employees Personal vs. Area Sample Grab
vs. Integrated Sample More to consider WHO WHERE WHEN EVALUATION
(Quantitative) How Active vs. Passive vs. Direct Reading
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81 EVALUATION (Quantitative) Results may demonstrate Below OEL
Above OEL Need for more effective engineering or PPE controls The
potential hazards of an operation The need for safer work practices
Relative safety of the operation Effectiveness of controls
Effectiveness of safe work practices Company/regulatory
compliance
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CONTROLS Airborne Exposure Prevention Generation of airborne
contaminants Contact with the body
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83 CONTROLS Hierarchy of Controls Change the process to
eliminate hazard, use a less toxic chemical, use a less hazardous
process etc. Transfer waste in fume hoods, safety interlocks, lead
shielding, inert atmospheres, guarding, etc. Implement procedures
and policies, train employees, post warning signs, etc. Safety
glasses, goggles, chemical protective gloves and apron, face
shield, lab coats, etc.
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Typically a combination of methods used simultaneously Fume
hood Hood use training Chemical safety training Written SOP on
specific procedure Gloves, eye protection, lab coat Waste disposal
methods training CONTROLS Combination of Controls
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Work with researchers to eliminate waste stream 85 CONTROLS
Elimination / Substitution
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Use local exhaust snorkel Transfer waste in lab exhaust hood or
glove box Use plastic vs. glass containers Use bottle carriers
Sharps containers Plastic lined container Secondary containers
CONTROLS Engineering - Remove or isolate the hazard
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Material handling techniques Limits on container size RCRA /
DOT requirements Good housekeeping No eating / drinking at worksite
Personal hygiene Medical monitoring program 87 CONTROLS
Administrative
89 Summary Do your homework ANTICIPATION / RECOGNITIION
Toxicology / Health Effects How material effects the body Routs of
Entry How it enters the body Exposure Limits - How much is allowed
Physical Properties of Chemicals How will it behave
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90 HOW WILL IT BEHAVE What can you predict", in general, what
will happen to: Particulates generated when a bottle breaks The
vapors of liquids when you pour off waste A liquid when it is
spilled Mix different waste streams Do you need to sample? Summary
Qualitative vs. Quantitative Evaluation
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CONTROLS Summary - Prevention Generation of airborne
contaminants Contact with the body