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Chapter 3: Understanding and Communicating About Laboratory HazardsA. Section 3.1.1 Responding to Laboratory Emergencies

1. Incident 3.1.1.1 Reusing Gloves

2. How We Become Exposed to Hazardsa. Hazard = potential source of danger or harm (can’t eliminate)b. Exposure = coming into direct contact with a hazard (try to minimize)

i. Route of chemical exposures: contact with skinii. Routes of physical hazard exposure: hit by flying particle from an explosion

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3. Routes of Chemical Exposurea. Ingestion (Oral route): swallowing hazardous chemical

i. To be toxic, the chemical must be absorbed in the stomach or intestinesii. Avoidance is straightforward

- Don’t Eat or Drink in the Lab- Don’t Taste the Chemicals! (Chemists used to do this for analysis)

iii. Accidental ingestion can occur by contaminated objects (hand, pen, etc…)Saccharin sweetener was discovered this way

b. Contact with the Eyesi. Eyes are particularly sensitive organs exposed directly to the environmentii. Most labs have strict safety glasses or goggles policiesiii. Spills, splashes, and broken glass are common laboratory hazardsiv. You might feel safe to take them off because of what you are doing, but you

can’t predict what your lab mates might dov. More on Eye Protection in Chapter 7

c. Inhalation: breathing hazardous chemical into your lungsi. Gases can get directly into the bloodstream due to gas exchange in lungsii. Volatile liquids = those that easily vaporize at room temperature

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iii. Keep chemical bottles closed when not usingiv. Work with volatile liquids and toxic chemicals in a chemical fume hoodv. Homogeneous Mixtures: gaseous contaminants in (gaseous) air (same phase)

- Vapor Pressure (volatility) is correlated to boiling point

- Use the boiling point on the label to predict hazardous liquids

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vi. Heterogeneous Mixtures: solids or liquids in air (different phases)- Colloid or Aerosol = particles from 0.01 to 100 mm

- Likely to occur when opening bottles, pouring liquids, spills- Concentrated acids “fumes” above the liquid—open only in a hood- Occur when grinding solids, handling fine powders, mixing solids

vii. Dangers of Aerosols- May stay in the air for hours, contaminating you later- Deposited in lungs, where they may react or dissolve and be absorbed- Larger particles may end up stuck in mucous and be ingested later

viii. Avoiding Exposure- If you can smell it, you are being contaminated- Some chemicals smell strongly, so smelling may prevent large exposure- Others have weak odor—the exposure may be serious before you smell- Treat all chemicals as potential hazards, don’t wait until it stinks!

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d. Skin Exposure (dermal exposure)i. Most common route of chemical exposureii. Skin is actually good at protecting us from most chemicalsiii. Some chemicals react with the skin only; others are absorbed into bloodiv. Cuts or open wounds increase the danger of exposure—keep coveredv. Spilled chemicals: small particles may expose the next user, be sure to clean

up thoroughly, especially around balancesvi. Other safety precautions: wear gloves, lab coats, absorbent covering paper,

closed toe shoes, vii. Gloves

- Don’t have to wear them all the time- Make sure you pick the right kind for the hazard - More on this topic in Chapter 7

e. Exposure by Injectioni. Some advanced chemical techniques require syringes and needlesii. Biological labs may have to make injectionsiii. Broken glass can “inject” contaminants iv. Use extreme care when using syringes and needlesv. More on this topic in Chapter 4

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B. Section 3.1.2 Signs, Symbols, and Labels1. Incident 3.1.2.1 Acetic Acid Explosion

2. Tool, Toy, or HAZARD!a. Swimming pools, Fire, Airplanes, Cars, Medicines: Beneficial but Hazardousb. Chemicals are similarly useful but potentially dangerousc. Key: recognizing and respecting hazards before exposure or incidents

3. Chemical Names—avoiding mistaken identitya. IUPAC Nomenclature: one specific name per chemical structureb. Common Names still (and probably always will be) usedc. CAS (Chemical Abstracts Service) Number: a specific ID # for each compound

a. CH3CH2OCH2CH3 = ether, ethyl ether, diethyl ether = CAS# 60-29-7b. CAS # is listed on most chemical labels, often in square brackets: [60-29-7]c. www.chemindustry.com/apps/chemicals http://webbook.nist.gov/chemistry

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4. Chemical Labelsa. OSHA requires information about hazards of every chemical be on the label

i. Law requires “Principle Hazard”ii. Chemical may have other hazards not on the labeliii. Don’t let the Principle Hazard blind you to the other hazards!

b. Terms describing various types of hazards should be familiar to youc. Symbols and Pictograms for various hazards are also used

Department of Transportation(DOT) Placards for transportedmaterials

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5. Hazard Rating Systema. Several rating systems for various hazards exist; NFPA (National Fire Protection

Association) system is the most well-known: NFPA Diamondb. Lab conditions ≠ Fire Conditions—some chemicals aren’t as dangerous as labeled

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C. Globally Harmonized System for Classification and Labeling of Chemicals (GHS)1. Incident 3.2.1.1 Isopropanol Explosion

2. United Nations authorized GHS in 1992 to Standardize Chemical Labelinga. Similar to United States MSDS system, but with some differencesb. Voluntary for nations to adopt and usec. Allows global marketplace where purchaser knows what they are getting

GHS “Purple Book” contains information on the various hazards

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Each chemical is to be accompanied by an SDS (Safety Data Sheet)with 16 sections of hazard, handling, and disposal information. Much like USA’s MSDS System

Federal Regulation “HazCom 2012” regulates full adoption of GHS in U.S. by 2016.13

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D. Section 3.1.3 Material Safety Data Sheets1. Incident 3.1.3.1 Chemical Sensitivity

2. Infinite Number of Chemicalsa. CAS had numbered over 81,000,000 compounds by 2013b. Many have never been tested for toxicity:

a. $100,000 per chemical using ratsb. Tiny amount ever existed in one lab

c. Chemical suppliers report what they knowd. Rules don’t require full toxicity testseven if the chemical is bought/sold

3. Good News: most of what you encounter willbe known and toxicologically tested

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4. 1980 OSHA “Hazard Communication Standard” required Material Safety Data Sheetsa. Often called MSDS Sheetsb. Required to be supplied to all purchasers/users of sold chemicals

i. May be supplied as a paper copy (especially the first time you buy)ii. Access to MSDS over Internet is now ubiquitous

c. Most MSDS Sheets (although not required to) follow American National Standards Institute (ANSI) formati. GHS follows the exact same formatfor its “SDS” sheets

ii. Legally required, but may not be accurate

iii. Interesting to compare different suppliers

iv. Large chemical suppliers are generallyreliable: Sigma-Aldrich; Thermo-Fisher; etc…

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5. Using MSDS Sheets—general informationa. Primarily, you will want to find information about hazards of the compoundb. Also a good source for emergency responders as how to handlec. Information on how to dispose of chemicals is also valuabled. How to find Hazard Information on an MSDS

i. Match the label of the bottle to the MSDS Sheet to make sure it’s the right oneii. Hazard information is usually found near the beginning

- “Hazard Identification”- “Physical and Chemical Characteristics”- “Fire and Explosion Hazard Data”- “Reactivity and Stability Data”- “Health Hazard Data”- Look for: “Corrosive”, “Flammable”, “Toxic”, “Irritant”

iii. Section on Personal Protective Equipment needed for use or clean-up- Not always specific: “Use appropriate protective gloves”- For clean-up: “follow state and local protocols”

6. Critical Reading of MSDS Sheetsa. First source of information, but may need more specific helpb. Chemists often feels MSDS sheets overstate dangers: from NaCl MSDS sheet

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E. Section 3.2.3 Interpreting MSDS Information1. Incident 3.2.3.1 Isopropyl Ether Detonation

2. Gleaning Useful Information for Hazard Assessment from MSDS Sheetsa. MSDS Sheets focus on industrial, large scale use of chemicals, not lab scaleb. Types of information on the MSDS

i. Data: simple information like mp, bp, aqueous solubility (should be correct)- One study showed >50% of 150 MSDS sheets had incorrect health

information or exposure level information- 1997 report found only 11% of MSDS sheets were accurate on all four

areas studied: health effects, first aid, PPE, exposure limitsii. Recommendations about Safety Procedures, Medical Treatment, Disposal

- Useful for large industry, not the chemical lab- May not be specific enough (gloves)- May not be updated as new information is learned

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c. How MSDS Sheets are Writteni. Scientist and/or Physician may write sectionsii. Lawyers will write others: there job is to avoid liabilityiii. May have been written by a computer! Generic phrases correct but not useful

d. Examples of MSDS Sheets (or their use) gone wrongi. Banning of Styrofoam cups because “Dihydrogen Oxide” used in

manufactureii. Recommendation to flush eyes with water if exposed to “Saline Solution”iii. Recommendation to wear safety glasses and lab coat for deionized water

e. Don’t Dismiss Too Muchi. Sucrose (table sugar) plant: makes sense to wear goggles and dust maskii. Sucrose dust (like wheat dust) can explode with right ignition sourceiii. Ordinary chemicals can be hazardous under the right(wrong?) conditions

3. Format of the Typical MSDS Sheet: Chemical and Hazard Identification (sect. 1-3)a. Section 1: Chemical Product and Company Identification

i. Information: what it is and who made itii. Use: there for comparison to the product; contact info may be useful

b. Section 2: Composition/Information on Ingredientsi. Information: purity, CAS #, list of compounds in mixtureii. Use: needed for an emergency or to clean up a spill correctly

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c. Section 3: Hazards Identificationi. Information: warning terms, potential health effects, exposure routeii. Use: usually good on physical hazards, often lists so many health hazards

without specifying extent of danger that it is confusing or uselessiii. New GHS Hazard Classification: assigns appropriate relative hazard ratings

4. Emergency Measures (sect. 4-6)a. Section 4: First Aid Measures

i. Information: general procedures if exposed, some give specific info for doctorii. Use: lets you develop a plan, important for doing the right first aid steps

b. Section 5: Firefighting Measuresi. Information: flammable properties, fire extinguisher, explosion hazardsii. Use: lets you develop a plan, put out a fire, important for firefighters

c. Section 6: Accidental Release Measuresi. Information: what you should do for a spillii. Use: get correct spill kits, helps professional responders to a big spill

5. Managing This Hazard (sect. 7-8)a. Section 7: Handling and Storage

i. Information: industrial intent, general warnings (no flame), incompatiblesii. Use: usually very generic and not very helpful for a lab

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b. Section 8: Exposure Controls/Personal Protectioni. Information: ways to prevent exposure (ventilation, gloves, safety shield)ii. Use: more useful for employer, not specific enough for lab worker

6. Hazard Recognition/Assessment Information (sect. 9-12)a. Section 9: Physical and Chemical Properties

i. Information: just like it saysii. Use: risk of vapor, flammability etc…; may help plan an experiment (mp)

b. Section 10: Stability and Reactivityi. Information: conditions to avoid, incompatible chemicals, hazardous productsii. Use: critical to someone doing reactions, helpful to emergency responders

c. Section 11: Toxicological Informationi. Information: known toxicity and human exposure limits, acute and chronicii. Use: lets user determine risks of using this particular chemicaliii. May not be fully tested, especially chronic (long term effects)iv. Toxicity data changes with new data—check how old the MSDS is

d. Section 12: Ecological Informationi. Information: behavior in and effects on environmentii. Use: informs how you will dispose of it, helpful if a spill occurs

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7. Regulated Activities (sect. 13-15)a. Section 13: Disposal Considerations

i. Information: US EPA Resource Conservation and Recovery Act (RCRA) requires all hazardous waste disposal be regulated; how to dispose properly

ii. Use: often very generic (follow all state and local regulations), but may mean more to waste specialist than to you. Don’t pour stuff down the sink!

b. Section 14: Transport Informationi. Information: US Dept. Transportation regulates shipping hazardous materials,

tells about how to label and shipii. Use: mostly for someone shipping materials elsewhere, must follow rules

c. Section 15: Regulatory Informationi. Information: specific rules for regulated chemicals, reporting spills if too bigii. Use: employer and EHS staff most concerned

8. Other Information (sect. 16)i. Information: date of last revision, references, hazard ratings, disclaimersii. Use: hazard ratings are more specific, make sure using most recent MSDS

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F. Section 3.2.2 Information Resources about Laboratory Hazards and Safety1. Incident 3.2.2.1 Dimethyl Sulfate and Sodium Azide Explosion

2. Internet Resourcesa. Google? Lots of misinformation (Google Scholar would be better)b. Wikipedia? Better, but still subject to errors (user produced encyclopedia)c. Recommendation: use reviewed material only when safety is at stake

i. MSDS Sheets can easily be found on-lineii. They have to exist, they don’t have to be correctiii. Table 3.2.2.1 Lists many web sites with Reviewed Safety Information

- Journal of Chemical Education- Sigma-Aldrich (on-line, or the printed catalog)- Chemical and Engineering News

3. Printed Resources: a number of well-known books on laboratory hazardsResearch the reaction or technique BEFORE you do it (not after a problem occurs)

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G. Section 3.3.1 Chemical Hygiene Plans1. Incident 3.3.1.1 Hydrofluoric Acid Exposure

2. Planning to Succeeda. Industrial Setting: large amounts of the same few chemicals for many yearsb. Laboratory Setting: Hundreds of compounds, used intermittently or only oncec. OSHA: Employees are required by law to have a workplace free from hazardsd. Students are not covered: moral and ethical reasons (not legal) to keep them safee. 1990 OSH “Lab Standard” performance standard for Academic Labs

- They don’t tell you how to limit exposure- They will test to see if you are and/or punish you if you aren’t (accident)

3. Chemical Hygiene Plan (CHP)a. OSHA Requires; available to employees; How do we keep our staff/students safeb. Chemical Hygiene Officer (CHO): responsible for the developing and implementing the CHP (Tom

Willis (recently retired), was SWOSU Dept. of Safety, Risk Management & Workers' Compensation)

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c. Recommended CHO Dutiesi. Develop CHP and appropriate measures for handling chemicalsii. Oversee the purchase, use, and disposal of chemicalsiii. Ensure adequate safety inspections and operationsiv. Assist in incident investigationv. Understand legal requirements