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Pyrophoric and air/water sensitive chemical hazards Neal Langerman Advanced Chemical Safety San Diego, CA
NATURE OF PROBLEM Safely handling highly reactive chemicals in a dynamic, competitive research environment (Apparent) increased use of pyrophoric and reactive chemicals in synthetic chemistry research Increased awareness of chemical safety at the institutional level Increased information sharing about incidents No method to determine if incidents (number or severity) has changed over time Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
 Page 3 Chemical Reactivity Hazards Air/Water/Pyrophoric Chemicals Silane release Cylinder in a gas cabinet Apparatus in open lab area Student adjusting apparatus initiated release Minor injuries Loss of lab
Air/Water/Pyrophoric Chemicals Thermal reflux/distillation Sodium metal THF  Student adjusted jammed overhead stirrer while system was hot Round-bottom cracked, releasing contents into hood Student burned Lab destroyed Building closed to 7 days 4 EH&S “terminated” over next months
Air/Water/Pyrophoric ChemicalsC&EN 22 Jan 2009 Researcher Dies After Lab Fire UCLA research assistant burned in incident with tert-butyl lithium Pyrophoric liquid Working alone during shutdown Chemical Reactivity Hazards  Page 5
Air/Water/Pyrophoric Chemicalstert-Butyl Lithium A 23 year old female research associate/laboratory technician intended to add an (unknown) aliquot of 1.6 M t-Bu-Li (in pentane) to a round bottom flask, placed in a dry ice/acetone bath.  She had been employed in the lab for about 3 months.  Limited experience with pyrophors Attempted to transfer 160 mL with successive aliqouts in a 50 mL plastic syringe Somehow, the syringe plunger popped out or was pulled out of the syringe barrel, splashing the employee with t-Bu-Li and pentane.  Ignited 4 L bottle of hexane in hood The mixture caught fire, upon contact with air.  She was wearing Nitrile gloves, safety glasses and synthetic sweater. She was not wearing a lab coat.  The fire ignited the gloves and the sweater. Chemical Reactivity Hazards  Page 6
Air/Water/Pyrophoric ChemicalsMost authoritative report Jyllian Kemsley, Ph.D., C&EN Reporter http://pubs.acs.org/cen/science/87/8731sci1.html Chemical Reactivity Hazards  Page 7
UCLA Update 12 March 2010 CAL/OSHA cites campus for failure to report 2007 injury to TA (employee)/Grad Student in Chemistry & Biochemistry CAL/OSHA cites campus for ongoing violations following the 2009 fatality Campus announces its intention to contest the citations Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals Reactive Safety
UCLA Update 17 March 2010 2007 Lab Fire Biochem grad student seriously burned when alcohol spill ignited by Bunsen burner 7 days in hospital Student was paid UCLA employee Chemical Reactivity Hazards  Page 9
UCLA Update 17 March 2010 Citations Failure to report injury Failure to correct unsafe working conditions Flammable liquid and open flame Inadequate PPE  No lab coat, insufficient clothing  Proposed fine: $29,300 Chemical Reactivity Hazards  Page 10
UCLA Update 17 March 2010 Follow-up inspection of Chemistry & Biochemistry Prompted by complaints from (unionized) university employees UCLA plans to contest both sets of citations Chemical Reactivity Hazards  Page 11
UCLA Update 17 March 2010 Chemical Reactivity Hazards  Page 12
During the past ten days: UCSD terminated the campus CHO Allegedly due to budget constraints The UCSD Director of EHS resigned on very short notice Reportedly is taking a position at Ann Arbor Money is “found” to re-hire the CHO No relationship to UCLA has been established UCSD Update Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Topic (from title page)
Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Common sense is not common Air/Water/Pyrophoric Chemicals The incident Sodium was used in an organic synthesis reaction Knife used to cut Sodium was rinsed in a regular sink with Methanol Piece of Sodium hit water in sink, igniting the Methanol Fire spread to 20 liter poly bottle of Acetone on shelf above sink Bottle burst
Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Common sense is not common Air/Water/Pyrophoric Chemicals The incident, continued A burning pool of acetone spread over lab Excess quantities of solvents ignited Two labs totaled Major flooding & smoke damage $750,000 property loss No injuries Same incident occurred 10 years later at another major research center
MANY CAUSES:SOME COMMON THEMES Insufficient training/Insufficient supervision Intense time/productivity pressure Safety institutionalized/Safety not functional at the lab level Academic culture rewards productivity with no attention to safety Safety must be given the same priority in academic culture given to publications and funding Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
What must be done? EHS – Shift responsibility for safety to PI’s Make it very clear that EH&S are consultants, not the “Safety Cops” Change the culture by shifting responsibility Get Provost-level support CAMPUS Include “safety performance” in PI evaluation Teaching Grants & Funding Lab Space Tenure Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
What must be done? National Give CSB Funding/Authority to investigate laboratory-scale incidents Place “Safety Performance” at an equal level of importance as research performance Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
What must be done? The Chemical Safety Community Define “Safety Performance” Lead rather than push And before ending … Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
Questions - Comments Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals

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Pyrophoric Chemicals

  • 1. Pyrophoric and air/water sensitive chemical hazards Neal Langerman Advanced Chemical Safety San Diego, CA
  • 2. NATURE OF PROBLEM Safely handling highly reactive chemicals in a dynamic, competitive research environment (Apparent) increased use of pyrophoric and reactive chemicals in synthetic chemistry research Increased awareness of chemical safety at the institutional level Increased information sharing about incidents No method to determine if incidents (number or severity) has changed over time Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
  • 3. Page 3 Chemical Reactivity Hazards Air/Water/Pyrophoric Chemicals Silane release Cylinder in a gas cabinet Apparatus in open lab area Student adjusting apparatus initiated release Minor injuries Loss of lab
  • 4. Air/Water/Pyrophoric Chemicals Thermal reflux/distillation Sodium metal THF Student adjusted jammed overhead stirrer while system was hot Round-bottom cracked, releasing contents into hood Student burned Lab destroyed Building closed to 7 days 4 EH&S “terminated” over next months
  • 5. Air/Water/Pyrophoric ChemicalsC&EN 22 Jan 2009 Researcher Dies After Lab Fire UCLA research assistant burned in incident with tert-butyl lithium Pyrophoric liquid Working alone during shutdown Chemical Reactivity Hazards Page 5
  • 6. Air/Water/Pyrophoric Chemicalstert-Butyl Lithium A 23 year old female research associate/laboratory technician intended to add an (unknown) aliquot of 1.6 M t-Bu-Li (in pentane) to a round bottom flask, placed in a dry ice/acetone bath. She had been employed in the lab for about 3 months. Limited experience with pyrophors Attempted to transfer 160 mL with successive aliqouts in a 50 mL plastic syringe Somehow, the syringe plunger popped out or was pulled out of the syringe barrel, splashing the employee with t-Bu-Li and pentane. Ignited 4 L bottle of hexane in hood The mixture caught fire, upon contact with air. She was wearing Nitrile gloves, safety glasses and synthetic sweater. She was not wearing a lab coat. The fire ignited the gloves and the sweater. Chemical Reactivity Hazards Page 6
  • 7. Air/Water/Pyrophoric ChemicalsMost authoritative report Jyllian Kemsley, Ph.D., C&EN Reporter http://pubs.acs.org/cen/science/87/8731sci1.html Chemical Reactivity Hazards Page 7
  • 8. UCLA Update 12 March 2010 CAL/OSHA cites campus for failure to report 2007 injury to TA (employee)/Grad Student in Chemistry & Biochemistry CAL/OSHA cites campus for ongoing violations following the 2009 fatality Campus announces its intention to contest the citations Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals Reactive Safety
  • 9. UCLA Update 17 March 2010 2007 Lab Fire Biochem grad student seriously burned when alcohol spill ignited by Bunsen burner 7 days in hospital Student was paid UCLA employee Chemical Reactivity Hazards Page 9
  • 10. UCLA Update 17 March 2010 Citations Failure to report injury Failure to correct unsafe working conditions Flammable liquid and open flame Inadequate PPE No lab coat, insufficient clothing Proposed fine: $29,300 Chemical Reactivity Hazards Page 10
  • 11. UCLA Update 17 March 2010 Follow-up inspection of Chemistry & Biochemistry Prompted by complaints from (unionized) university employees UCLA plans to contest both sets of citations Chemical Reactivity Hazards Page 11
  • 12. UCLA Update 17 March 2010 Chemical Reactivity Hazards Page 12
  • 13. During the past ten days: UCSD terminated the campus CHO Allegedly due to budget constraints The UCSD Director of EHS resigned on very short notice Reportedly is taking a position at Ann Arbor Money is “found” to re-hire the CHO No relationship to UCLA has been established UCSD Update Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Topic (from title page)
  • 14. Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Common sense is not common Air/Water/Pyrophoric Chemicals The incident Sodium was used in an organic synthesis reaction Knife used to cut Sodium was rinsed in a regular sink with Methanol Piece of Sodium hit water in sink, igniting the Methanol Fire spread to 20 liter poly bottle of Acetone on shelf above sink Bottle burst
  • 15. Advanced Chemical Safety www.chemical-safety.com Solutions@chemical-safety.com Common sense is not common Air/Water/Pyrophoric Chemicals The incident, continued A burning pool of acetone spread over lab Excess quantities of solvents ignited Two labs totaled Major flooding & smoke damage $750,000 property loss No injuries Same incident occurred 10 years later at another major research center
  • 16. MANY CAUSES:SOME COMMON THEMES Insufficient training/Insufficient supervision Intense time/productivity pressure Safety institutionalized/Safety not functional at the lab level Academic culture rewards productivity with no attention to safety Safety must be given the same priority in academic culture given to publications and funding Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
  • 17. What must be done? EHS – Shift responsibility for safety to PI’s Make it very clear that EH&S are consultants, not the “Safety Cops” Change the culture by shifting responsibility Get Provost-level support CAMPUS Include “safety performance” in PI evaluation Teaching Grants & Funding Lab Space Tenure Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
  • 18. What must be done? National Give CSB Funding/Authority to investigate laboratory-scale incidents Place “Safety Performance” at an equal level of importance as research performance Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
  • 19. What must be done? The Chemical Safety Community Define “Safety Performance” Lead rather than push And before ending … Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals
  • 20. Questions - Comments Reactive Safety Advanced Chemical Safety www.chemical-safety.com solutions@chemical-safety.com Air/Water/Pyrophoric Chemicals