recognizing, evaluating, and controlling chemical hazards to reduce occupational exposure to...

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

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

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.

Apply industrial hygiene concepts 4 ANTICIPATION RECOGNITION EVALUATION CONTROL TAKE A WAY Predict your exposure to airborne hazardous waste

5 ANTICIPATION RECOGNITION EVALUATION CONTROL INDUSTRIAL HYGIENE Four Fundamental Elements

6 ANTICIPATION RECOGNITION EVALUATION CONTROL Anticipation/recognition of potential or actual hazards cradle-to-grave concept (research through waste disposal) INDUSTRIAL HYGIENE Anticipation Proactive

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

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

9 ANTICIPATION RECOGNITION EVALUATION CONTROL Methods to eliminate or reduce exposure Elimination / Substitution Engineering Controls Administrative Controls PPE Control Prevention INDUSTRIAL HYGIENE

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

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

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

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

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

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

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?

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

Dose Rate of generation Physical state Temperature Genetics Site of contact with body General health of individual 18 TOXICOLOGY Response depends on many factors

Skin irritation - Reversible damage -Acetonitrile (Skin irritation 3) * Skin corrosion - Irreversible tissue damage -Grignard reagents (Skin corrosion - 1B) * Eye Irritation Reversible damage -Graphite flakes (Eye Irritation - 1B) * Serious Eye Damage Irreversible tissue damage -Hydrazine (Seri Eye Dam - 1) * ACUTE EFFECTS High concentration, short duration, short response time 2012 HazCom Terms *Source: Sigma Aldrich

Single or multiple dose of a substance ~ 4- 24 hrs. Cat 1: LD 50 (oral) -- oral dose/rats 5 milligrams per kilogram (mg/kg) -Dimethyl mercury (Acute Tox 1, Dermal) * Cat 2: LD 50 (oral) -- oral dose/rats > 5 and 50 mg/kg - Mercury nitrate monohydrate (Acute Tox 2, Oral) * Cat 3. LD 50 (oral) -- oral dose/rats > 50 and 300 mg/kg -Nickel chloride (Acute Tox 3, Oral) * Cat 4. LD 50 (oral) -- oral dose/rats > 300 and 2000 mg/kg -Potassium perchlorate (Acute tox 4, Oral) * ACUTE EFFECTS Acute Toxicity (Oral, Dermal, Inhalation) 2012 HazCom Terms *Source: Sigma Aldrich

ACUTE EFFECTS Perspective *Source: Prudent Practices, Cat. 1 Cat. 2 Cat. 3 Cat. 4

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

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

24 ADDITIVE 2 + 2 = 4 ADDITIVE 2 + 2 = 4 ANTAGONISTIC 3 + (-2) = 1 ANTAGONISTIC 3 + (-2) = 1 SYNERGISTIC 2 + 2 = 10 SYNERGISTIC 2 + 2 = 10 POTENTIATING 2 + 0 = 10 HEALTH EFFECTS

Occupational Routes of Entry Inhalation Skin contact/skin absorption Ingestion Injection 25 Contact with the body ROUTES OF ENTRY

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.

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.

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.

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

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

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

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

Noise Heat Stress Cold Stress Vibrations Ionizing Radiation Non-Ionizing Radiation 33 EXPOSURE LIMITS Also for physical hazards

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

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

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

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

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

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

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)

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

Knowledge of the physical state of matter can help anticipate its movement in the air near your Breathing Zone. 42

43 PHYSICAL PROPERTIES Physical States of Matter

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

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

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

47 Can: Be toxic and corrosive Be absorbed through the skin and mucus membranes Cause contact related health effects Liquids flow LIQUIDS

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

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

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

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

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.

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

54 Health Effects Toxicology How Chemicals Behave Chemical Compatibility Chemical Compatibility Exposure Routes Exposure Limits Summary ANTICIPATION / RECOGNITIION

Based on your of knowledge: How stressors might behave Now they may interact with your body 55 Evaluate your potential exposure EVALUATION

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

RECOGNITION 57 Judgment on whether a worker will be exposed over the OEL or conservatively, the OEL (action level) EVALUATION (Qualitative) Qualitative Exposure Assessment

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)

59 Environmental Stressor Properties must be weighed against the Risks Factors EVALUATION (Qualitative) Airborne Exposure Assessment

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

RECOGNITION Ask yourself: What type of limit? Combination Different concentrations 61 EVALUATION (Qualitative) Stressor Properties 8 Hr TWA 15 Min STEL 10 Min Ceiling

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

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.

ChemicalOdor LowOdor HighDescriptionIrritating Conc. Exposure Limit (ACGIH) Acetone20 ppm679 ppmMisty Chemical, Sweet 200 ppm500 ppm 8 hr 750 ppm - STEL Benzene1.4 ppm85 ppmSweet, solvent2,800 ppm0.5 ppm 8 hr 2.5 ppm - STEL Ethyl Benzene2.0 ppm200 ppmAromatic200 ppm100 ppm 8 hr 125 ppm - STEL Hydrogen Sulfide 0.0005 ppm 0.01 ppmRotten eggs10 ppm5 ppm 8 hr 15 ppm - STEL Perchloro- ethylene 4.6 ppm69 ppmChlorinated solvent 200 ppm25 ppm 8 hr 100 ppm - STEL Toluene2.0 ppm40 ppmRubbery, mothballs 200 ppm50 ppm 8 hr Xylene0.08 ppm40 ppmSweet100 ppm100 ppm 8 hr 150 ppm - STEL Selected Odor Thresholds To be used as guidelines only Are subjective and differ from person to person

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?

Ask yourself: Whether you may be exposed over the OEL using Risk Factors as a guideline 66 EVALUATION (Qualitative) Stressor Properties

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

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

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

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

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?

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

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

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

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

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)

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

EVALUATION (Quantitative) 78 Quantitative Exposure Assessment Measurement of the stressor for comparison to OELs Must be conducted by an experienced Industrial Hygienist

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

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

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

CONTROLS Airborne Exposure Prevention Generation of airborne contaminants Contact with the body

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.

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

Work with researchers to eliminate waste stream 85 CONTROLS Elimination / Substitution

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

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

88 CONTROLS Personal Protective Equipment Gloves Lab coat / Apron / Tyvek Face shield / goggles Respiratory protection Proper removal /disposal Decontamination

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

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

CONTROLS Summary - Prevention Generation of airborne contaminants Contact with the body

Thank You, Any Questions? 92

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