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3/11/16
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Common Laboratory Hazards
Rich Wittman, MD, MPH Clinical Assistant Professor [email protected]
Medical Director, Stanford and SLAC Occupational Health Centers
Disclosures
I have nothing to disclose
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Goals
§ Stress the global importance of iden:fying laboratory hazards in your workplace, using this knowledge to dictate safety policy and goals
§ Provide an overview of higher-‐profile lab safety incidents
§ Convey the significant impact of a single adverse lab event, and the ease of such an occurrence
§ Discuss an approach for addressing ins:tu:onal risk as it pertains to the lab research environment
Prac:cal Toxicology § All substances are poisons; there is none which is not a poison. The right dose
differen8ates a poison from a remedy -‐-‐Paracelsus, 1567 § 2007: Jury rules against radio sta:on aNer woman dies in water drinking contest § 2012: Tragic case involving 12-‐year old following a game of “water poker”
§ Precau:onary Principle § Protec:ve ac:ons can and should be taken before defini:ve proof has been
established of poten:al harm from use of any chemical with suspected toxic impacts on human or environmental health
§ In 2003, San Francisco became the first U.S. city to adopt a Precau:onary Principle ordinance, sta:ng:
“Where threats of serious or irreversible damage to people or nature exist, lack of full scien:fic certainty about cause and effect shall not be viewed as sufficient reason…to postpone cost effec:ve measures to…protect the health of its ci:zens..”
§ Risk stra:fica:on § Where does this leave us? Relying on common sense and pragma:sm, or
paranoid?
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Risk Stra:fica:on of Lab Hazards § What is your knowledge base?
§ Preven:on requires a baseline awareness of poten:al risk, toxic or otherwise § Soda and diabetes § Bleach and ammonia § Arsenic and brown rice
§ What is the end point or outcome of interest? § Acute or chronic?
Chemical burn / neoplas:c agent risk
§ High visibility, high impact, or high likelihood? Pyrophoric agent / formaldehyde splash
§ The risk-‐assessment relies on the breadth and scope of the health and safety vision AND in:mate knowledge of the research processes Ø This requires subject maber expert and line-‐level input
Chemical Safety
Lab Safety
Biosafety
Hazardous Materials
Ergonomics
Occupa:onal Health
Compliance and Safety Assistance
Industrial Hygiene
Interdepartmental communica8on
Who contributes to your risk assessment?
What is your mechanism for integra8ng and assessing these risks?
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High-‐risk, high visibility incidents
§ Pyrophorics § Can spontaneously ignite in air at temps <130°F
§ Gases: stored in compressed gas cylinders § Liquids: metal hydride/alkyl/carbonyl/vinyl stored in a hydrocarbon solvent (THF,
pentane, heptane) § Solid: Metal stored in oil
§ Highly reac:ve with air (oxygen) and water (moisture) § Handled in inert condi:ons (argon/nitrogen) § Flame-‐dry glassware cooled in inert atmosphere
§ Act as strong base and H+ remover (deprotona:on)
Organolithium handling
§ Schlenk line technique § Air ‘removal’ from needle and syringe § Draw up reagent into syringe § Draw up inert gas into needle/syringe
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Organolithium handling
§ PPE § Nitrile gloves, inner layer § 2nd layer of chemical-‐resistant, silver shield gloves § Flame-‐resistant lab coat, long pants, closed-‐toe shoes § Tight-‐finng goggles, full face shield
§ Emergency response § Immediate use of emergency shower § Dry chemical fire ex:nguisher: Can be applied in presence of people
§ Pyro Chemical Purple K (PK): Potassium bicarbonate § Standard ABC Dry Chemical: Sodium bicarbonate
§ Soda ash (sodium carbonate) or dry sand (SiO2)
Pyrophorics and energe:c materials
UCLA, 2008 tert-‐Butyllithium (t-‐BuLi)
Fatal injury following tBuLi air exposure with severe burns to lab assistant
• Using nitrogen method in hood, 50 ml aliquots in 60 ml syringe
• Syringe plunger came out of the barrel
• Open flask of hexane in hood
• PPE incomplete
• No buddy system
• 911 response 7 minutes
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• Experiment: No formalized training on pyrophorics. Use of 2” needle rather than recommended 1-‐2 foot needle cannula; plas:c not glass syringe • PI: No documented ins:tu:onal training /guidance in lab set up
Training
• Experiment: No lab coat; use of synthe:c clothing, glasses not goggles
• Lab: Mul:ple members without appropriate PPE PPE
• Experiment: Working ‘alone’ during Holiday break • University: Chemical safety review noted deficiencies prior to accident, lab missed 30-‐day deadline to address without penalty
Supervision/ Oversight
• Experiment: No emergency shower use; no dry chemical fire ex:nguisher
• Lab: Smaller loca:on with reduced storage during renova:ons, improper flammable material storage
Work Planning and Control
• University: Prior burn injuries in labs, no lab coat use; No ac:onable change • 2007: Ethanol and Bunsen burner • 2008, 1 week before t-‐BuLi: localized explosion
Culture
UCLA, 2008
Pyrophorics and energe:c materials
Texas Tech, 2010 ~Nickel hydrazine perchlorate
(NHP)
Grad student with loss of 3 fingers and permanent ocular injury
• White crystalline solid, can be detonated by shock or fric:on; more stable when ‘wet’
• Synthesis part of Department of Homeland Security research on energe:c materials and IEDs
• Ini:al synthesis, up to 300 mg; opted to synthesize 10 grams
• Product was clumping and did not appear uniform; chose to grind
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• Experiment: Senior grad student helping train 1st-‐year student • Labs: Most chemistry grad students had not taken general lab safety training
Training
• Experiment: Use of goggles at sta:on ini:ally; walked away and returned without eyewear
• Lab: Mul:ple members reported use of eye PPE a personal choice based upon risk of experiment
PPE
• Experiment: Students independently chose to scale up produc:on due to amount of compound needed and variability between batches
• University: Review of energe:c work not effec:vely assessed. Safety officials did not report to those with authority to facilitate change
Supervision/ Oversight
• Experiment: No hazard evalua:on regarding the use of water or hexane to mi:gate explosive hazard with high quan:ty NHP
• PI: No mechanism to ensure communica:on regarding strict 100 mg limit on produc:on of energe:c materials
Work Planning and Control
• Chemistry Group: Two near misses in same lab region previously
• Campus: Prior lab incidents not consistently documented or formally communicated, preven:ve lessons not disseminated
Culture
Texas Tech, 2010
These incidents represent systemic failures
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Safety Review of Near
Misses and Incidents
Chemical Inventory System
RadiaUon, Toxins, and Biologic Agents
PPE and Risk training
Ergonomics
Safety Compliance
and Assessment
How complete is your safety/risk assessment?
What is your tool for integra8ng and assessing these risks?
Water-‐reac:ve chemicals (WRC)
Boston College 2011: Beaker with thionyl chloride exploded resul:ng in arm lacera:on and eye injury
§ Reacts violently with moisture in highly exothermic reac:on SOCl2 + H2O → 2 HCl + SO2
§ SO2: Inhala:on leads to immediate upper airway irrita:on SO2 + H2O → H2SO3 (sulfurous acid)
§ Eye, nose, throat burning, cough, wheezing, laryngospasm ▫ 10 ppm coughing; 20 ppm bronchospasm ▫ Watch for delayed pulmonary symptoms
Colorado College 2013: 13 hospitalized when canister exploded when students drilled into pressurized container to obtain Utanium tetrachloride, TiCl4
§ Liquid at room temp, it reacts strongly with moisture TiCl4 + 2 H2O → TiO2 + 4 HCL
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Nitric Acid (HNO3) § Strong oxidizing agent, can react violently with organic solvents (TNT)
§ Can cause igni:on of combus:ble material, can react violently with water
§ Nitra:ng mixture: Nitric acid mixed with sulfuric acid, which helps catalyze certain reac:ons
Dermatologic exposure
§ Direct skin contact leads to :ssue damage with a characteris:c yellow staining § [HNO3]: Superficial burns in 5 seconds, full thickness aNer 30 seconds § Penetra:on into deeper layers (e.g HF) does not occur
Nitric Acid (HNO3) § Nitrogen dioxide (NO2)
§ Forms following reac:ons primarily involving concentrated nitric acid C + 4 HNO3 → CO2 + 4 NO2 + 2 H2O
§ Lung injury § NO2 forms nitric acid on contact with water § Less soluble in water, deeper penetra:on into lungs more likely
§ Reaches lower airways: pneumoni:s, bronchioli:s, ARDS § More likely than SO2 to produce delayed symptoms aNer > 12 hrs
§ SOB and cough characteris:c § Poten:al for acute to subacute tachycardia, wheezing, cyanosis § Poten:al for onset of pulmonary edema following minimal ini:al symptoms
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Strong acids
§ USC, 2003: Lab assistant pouring boble of nitra:ng mixture (nitric and sulfuric acids) in a fume hood when it broke, cascading onto her thighs and the floor. § Hospitalized with 3rd degree burns
§ Immediately removed clothing and shoes and splashed some water on the area § Shortly aNer was placed in safety shower by supervisor
§ Texas Tech, 2011: An organic solvent mixture was (likely) added to a 2.5 L waste boble of 25-‐30% nitric acid. Catastrophic failure of the sealed acid glass storage boble from over-‐pressuriza:on led to explosion and shrapnel up to nearly 60 feet away
Distance away shrapnel travelled
Texas Tech, 2011
Crack in fume hood countertop
ContribuUng factors • Work planning and control
• Fume hood sash itself leN mostly open • Waste boble management
• Contents not clearly marked and not disposed of in :mely fashion • Bobles not polymer-‐coated to minimize fragmenta:on • No ven:ng caps
• Excess chemical and reagent bobles not in use were stored in fume hood
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Strong acids
§ University of Maryland, 2011 § Two students in sophomore organic chem lab added nitric/sulfuric acid
mixture to waste container with organic reagents § Treated for 1st and 2nd degree chemical burns
§ Princeton, 2012 § Chemical burns on face and bodily contusions aNer container broke inside a
chemical cabinet—a solvent had been added to nitric acid leading to explosion § With use of eye and hand PPE
ColoraUon of nitric acid burn →
University of Maryland, 2011
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Case example, post-‐exposure § 50 year-‐old life science researcher presents for evalua:on due to persistent headaches following work in the lab. Notes occurs intermibently but now triggering migraine with aura. With reduced sleep lately due to work and home stress.
Outcome 1: Pa:ent with known migraines and clear stressors Ø Referred to primary physician for follow-‐up
Outcome 2: Employee asked about poten:al trigger at work and reports lab member who works with chemical on a lab bench rather than the hood
Ø Contacted lab manager who reports no odor in lab, just typical organic odors intermibently. Commented that no one else seems bothered but the employee is more sensi:ve to odors than most.
Outcome 3: Industrial hygiene contacted for in-‐depth follow-‐up
Ø No odor in lab detected in lab during visits Ø Interviews revealed named coworker apparently using mercaptoethanol outside of hood and possibly with disposal in regular trash receptacle
Ø Provided educa:on and counselling and tasked disposal monitoring to compliance team.
Case example, post-‐exposure § 2-‐Mercaptoethanol or β-‐mercaptoethanol (HOCH2CH2SH)
§ Used in labwork to reduce/cleave disulfide bonds before gel electrophoresis § Improves survival or neuronal cultures § Low odor threshold, similar to odor used in natural gas
§ Work required in chemical fume hood or 100% exhausted BSC § Respiratory effects: Irritant vapors with resultant cough to shortness of breath
§ ½ or full-‐face respirator if work performed outside of hood
§ Case follow-‐up § History revealed prior exposure for employee when a boble of MCE dropped
and broke 10 years prior § Local area evacuated § Employee missed one month of work
§ Headaches § Chemical odor sensi:vity § Respiratory complaints
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How robust is your culture of safety?
Interfacing with the lab
Role of Health and Safety Professionals
Walk around the lab and be present and engaged
Demonstrate and model the culture of safety
Address barriers to PPE use
Help lab members see the bigger picture
Increase hands-‐on training over click-‐through online classes
Provide orienta:on to PIs and clear SOP guidelines
Encourage buddy system and lab safety partnerships
Educate that a near-‐miss is an incident
Do you educate and empower..or react and rec8fy?
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§ AkzoNobel, Technical Bulle:n, Control of Metal Alkyl Fires. Retrieved Feb 201 from hbps://www.akzonobel.com/hpmo/system/images/AkzoNobel_Control_of_metal_alkyl_fires_ma_glo_eng_tb_tcm36-‐14977.pdf. Date of Publica:on Aug 2008.
§ ATSDR, Medical Management Guidelines for Nitrogen Oxides, CAS 10102-‐43-‐9. Retrieved Feb 2016 from hbp://www.atsdr.cdc.gov/mmg/mmg.asp?id=394&:d=69. Date of last update, 2014.
§ ATSDR, Toxicological Profile for Sulfur Dioxide, CAS 7446-‐09-‐5. Retrieved Feb 2016 from hbp://www.atsdr.cdc.gov/toxprofiles/tp.asp?id=253&:d=46. Date of Publica:on 1998.
§ ATSDR, Toxicological Profile for Titanium Tetrachloride, CAS 7550-‐45-‐0. Retrieved Feb 2016 from hbp://www.atsdr.cdc.gov/toxprofiles/tp.asp?id=664&:d=122. Date of Publica:on 1997.
§ Government of Alberta, Canada. Handbook of Occupa:onal Hazards and Controls for Laboratory Workers. Retrieved Feb 2016 from hbps://work.alberta.ca/documents/OHS-‐WSA-‐handbook-‐laboratory-‐workers.pdf. Date of Publica:on 2011.
§ Kolios L, Striepling E, Kolios G, Rudolf KD, Dresing K, Dörges J, Stürmer KM, Stürmer EK. The nitric acid burn trauma of the skin. J Plast Reconstr Aesthet Surg. 2010 Apr;63(4):e358-‐63.
§ Mar:n, Jared, Incident Report Oct 14, 2011, Texas Tech University Environmental Health & Safety. Retrieved Feb 2016 from hbps://www.depts.bu.edu/vpr/integrity/csb-‐response/downloads/Incident-‐Report-‐for-‐Chemistry-‐332-‐10.14.2011.pdf. Date of publica:on Nov 2011.
§ NASA. New NASA Images Highlight U.S. Air Quality Improvement. Retrieved Feb 2016 from hbps://www.nasa.gov/content/goddard/new-‐nasa-‐images-‐highlight-‐us-‐air-‐quality-‐improvement/. Date of Publica:on June 2014
§ Prince George’s County, Fire/EMS Department News. Retrieved Feb 2016 from hbp://pgfdpio.blogspot.com/2011/09/university-‐of-‐maryland-‐chemical.html. Date of Publica:on Sep 2011.
§ Texas Tech University, Communica:os Regarding Jan. 7, 2010 Accident. Retrieved Feb 2016 from hbp://www.depts.bu.edu/vpr/integrity/CSB-‐response/prior-‐communica:ons.php. Date of last update, Nov 2015.
§ University of California, Center for Laboratory Safety. Standard Opera8ng Procedure, Pyrophorics, Organolithium Reagents. Retrieved Feb 2016 from hbps://chemengr.ucsb.edu/~ceweb/faculty/scob/Chemical%20SOPs/OrganolithiumReagents.pdf. Date of Publica:on 2012.
§ UCLA Chemistry, Procedures for Safe Use of Pyrophoric Solids. Retrieved Feb 2016 from hbp://www.chemistry.ucla.edu/sites/default/files/safety/sop/SOP_Pyrophoric.pdf. Date of Publica:on Feb 2009.
§ UCLA, Environmental Health & Safety. Standard Opera8ng Procedure: 2-‐mercaptoethanol. Retrieved Feb 2016 from hbp://safety.healthsciences.ucla.edu/files/view/sop/2Mercaproethanol.doc. Date of Publica:on 2015.
§ University of Minnesota, Pyrophoric Chemicals Guide. Retrieved Feb 2016 from hbp://www.dehs.umn.edu/PDFs/Pyrophoric_Chemicals_Guide.pdf. § University of Nebraska-‐Lincoln, Chemistry Department & Environmental Health & Safety. Unstable, Reac8ve & Energe8c Chemicals. Retrieved Feb 2016
from hbp://ehs.unl.edu/training/colloquium/2012-‐04_Presenta:on.pdf. Date of Publica:on, 2007. § U.S. Chemical Safety and Hazard Inves:ga:on Board. Texas Tech University, Laboratory Explosion. No 2010-‐05-‐I-‐Tx. Retrieved Feb 2016 from
hbps://www.depts.bu.edu/vpr/integrity/csb-‐response/downloads/report.pdf. Date of Publica:on 2011. § U.S. Department of Labor, Accident Report Detail, Nitric Acid. Retrieved Feb 2016 from
hbps://www.osha.gov/pls/imis/AccidentSearch.search?acc_keyword=%22Nitric%20Acid%22&keyword_list=on.
References
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Pulmonary edema is more likely to occur following exposure to this agent?
§ A. Lithium Hydride
§ B. Sulfur Dioxide
§ C. Nitrogen Dioxide
§ D. Formaldehyde
Which is the simplest manner to improve lab safety?
§ A. Enforce and reward PPE use
§ B. Track near-‐miss incidents
§ C. Establish a culture of safety
§ D. Educate incoming PIs
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What is the best method to put out a fire sourced from a pyrophoric agent?
§ A. Submerse it in water
§ B. Dry chemical ex:nguisher
§ C. Carbon dioxide ex:nguisher
§ D. Low-‐frequency sound wave ex:nguisher
