Review of Extremely Hazardous Chemicals
Date: Oct. 21, 2019
Version: 01
Policy
Use of chemicals that present an extremely acute hazard to personnel health and safety, environmental health, or UNR facilities and physical assets beyond that associated with chemicals commonly used in laboratories requires standard operating procedures (SOPs) be developed and followed to ensure that the proposed work will be performed safely.
Responsible Authority
Vice President for Research and Innovation (VPRI); Environmental Health and Safety (EH&S) Department
Scope
This policy applies to chemicals and procedures identified in this policy as extremely hazardous and other chemicals that meet listed criteria as extremely hazardous when they are used in UNR laboratory facilities or when UNR employees or students are directly involved in handling of such chemicals. This policy also applies to chemicals not identified in this policy as extremely hazardous or which don’t meet listed criteria as extremely hazardous, but which the laboratory supervisor judges to be at a hazard level similar to chemicals and procedures listed in this policy.
Background
Health and safety regulations and the UNR Chemical Hygiene Plan require development of written health and SOPs that address the use of hazardous chemicals in laboratories. At UNR, use of radioactive materials and biological agents also requires development of SOPs, and additionally, work involving these materials must be reviewed by an independent UNR safety committee.
Although there are hazards associated with almost all laboratory chemicals, some are considered extremely hazardous due to acute toxicity, chemical reactivity, or instability. Such chemicals require special techniques and control measures in order to handle them within an acceptable level of risk, and analogous to radioactive materials and biological agents, an independent review of planned work is justified.
Chemicals which are judged to be extremely hazardous and justify independent review of planned work are listed in Appendix I. For work involving these chemicals a SOP must be submitted to EH&S.
Reference Regulations
29 CFR 1910.1450, Occupational Exposure to Hazardous Chemicals in Laboratories
Definitions
Explosive Chemical: Any chemical compound or mixture that, when subjected to heat, impact, friction, detonation, or other suitable initiation, undergoes rapid chemical change, evolving large volumes of highly heated gases that exert pressure on the surrounding medium. A list of functional groups commonly found in explosive chemicals is provided in Appendix II to assist in identifying explosive chemicals.
Pyrophoric chemical: Any chemical compound, element, mixture, or solution that ignites spontaneously on exposure to air. A list of common classes of pyrophoric chemicals is provided in Appendix II to assist in identifying pyrophoric chemicals.
LC50: the concentration of a chemical in air that on the basis of laboratory tests (via respiratory route) is expected to kill 50% of a group of test animals (rodents, generally rats) when administered as a single, one hour exposure.
LCLo: the lowest concentration of a chemical in air reported to have caused death.
LD50: the single dose of a chemical that causes death of 50% of an animal population from exposure to the chemical by any route other than inhalation (route must be specified).
LDLo: the lowest dose of a chemical introduced by any route other than inhalation, reported to have caused death.
Responsibilities
Deans, Department Chairs, and Directors
Ensure that laboratory supervisors are aware of the responsibilities and procedures contained in this policy, and provide administrative enforcement of this policy.
Laboratory Supervisors
Identify chemicals or chemical procedures considered to be extremely hazardous as outlined in this policy prior to acquisition of chemicals or initiation of procedures, as required by this policy.
Ensure that SOPs covering all chemicals and procedures listed in Appendix I that are either used by personnel for which they have supervisory responsibility, or which are stored in facilities for which they are responsible, are submitted to EH&S as described in the “Procedures” section of this policy.
Approve all SOPs that apply to chemicals used by personnel for which they have supervisory responsibility or which are stored in facilities for which they are responsible.
Address safety deficiencies identified by the Laboratory Safety Committee (LSC) or EH&S by implementing recommended changes or providing justification as to why the changes are not needed.
Take all reasonable measures to ensure compliance with the requirements and procedures included in submitted SOPs.
Ensure that all personnel who use or may be exposed to chemicals covered by this policy are adequately trained with regards to hazards, safe work procedures, personal protective equipment and other safety equipment, and incident response procedures, and that such training is documented.
Environmental Health & Safety Department
Provide management of the SOP review process, to include submittal, committee review, and records management.
As requested, provide assistance to laboratory supervisors in identifying chemicals and procedures covered by this policy, completing SOPs, and other assistance related to health and safety issues associated with these chemicals and procedures.
Review operations covered by SOPs on a periodic basis to ensure compliance with the specified requirements and procedures. Deviations should be brought to the attention of the laboratory supervisor. Issues of significant risk or which cannot be resolved directly with the laboratory supervisor should be reported to the LSC.
Laboratory Safety Committee
As requested by EH&S, review submitted SOPs in a timely manner and communicate recommendations to address safety deficiencies to the responsible laboratory supervisor.
Provide administrative oversight of safety issues associated with chemicals and procedures covered by this policy. Major issues of non-compliance with this policy should be reported to VPRI. Recommendations for resolution and administrative action may be included in such reports.
Periodically review and update Appendix I as needed.
Laboratory Personnel
Comply with the requirements and procedures specified in submitted SOPs that are applicable to chemicals that they handle or are exposed to, and procedures that they conduct.
Procedures
Each laboratory supervisor must submit to EH&S one or more SOPs that collectively describe safety and health procedures for all chemicals listed in Appendix I that are used by personnel for which they have supervisory responsibility or which are stored in facilities for which they are responsible.
SOPs for all chemicals listed in Appendix I which are currently in possession must be submitted no later than six months after the approval date of this policy, after which, SOPs must be submitted prior to acquisition of extremely hazardous chemicals or initiation of extremely hazardous procedures.
All SOPs must be specific for the laboratory facility and procedures in which they will be used. SOPs can be written to cover use of individual chemicals or a class of multiple chemicals for which the hazards and safety procedures are similar, or a procedure. Photos and diagrams should be included as appropriate to effectively communicate hazards and procedures.
Appendix II contains a template that may be used to prepare SOPs; however, other formats may be used as long as the topics included in Appendix II are incorporated. For example, the University of California Center for Laboratory Safety maintains a library of SOP templates, which can be accessed through the .
References
- Santa Clara County (California) Toxic Gas Ordinance, Common Toxic Gases as Defined by the Toxic Gas Ordinance and CFC, [Online] October 7, 2016.
- Urben, P. G. (ed.). Bretherick’s Handbook of Reactive Chemical Hazards, Fifth Edition – Volume 2, Butterworth-Heinemann Ltd.: Oxford, 1995; pp. S20 – S22; 123 – 124.
- U. S. Department of Labor, Occupational Safety and Health Administration, Globally Harmonized System of Classification and Labeling of Chemicals, [Online] October 7, 2016.
- Strem Chemicals Catalog No. 22, 2008-2010.
Related Material
Appendix I: Some Specific Examples of Extremely Hazardous Chemicals
Storage or use of any of the following chemicals requires submittal of a SOP to EH&S.
Acutely Toxic Chemicals
- Acutely Toxic by Dermal Exposure (chemicals that can cause serious or life-threatening harm as a result of a single dermal exposure that could reasonably occur during laboratory use).
Dimethylmercury, 1 to several drops lethal human dermal exposure
- Acutely Toxic Gases (LC50 or LCLo ≤ 100 ppm, 4 hour exposure)
Example Chemicals - list not all inclusive:
Arsine (AsH3), 178 ppm LC50 (1 hour), rat; 45 ppm LC50 (4 hour), rat
Diborane (B2H6), 80 ppm LC50 (1 hour, estimated), rat; 40 ppm LC50 (4 hour), rat
Fluorine, 185 ppm LC50 (1 hour), rat; 92.5 ppm LC50 (4 hour, estimated), rat
Hydrogen Cyanide, 150 ppm LC50 (30 min.), rat
Hydrogen Selenide, 6 ppm LC50 (1 hour), rat; 3 ppm LC50 (4 hour, estimated), rat
Nitric Oxide, 115 ppm LC50 (1 hour), rat; 57.5 ppm LC50 (4 hour, estimated), rat
Nitrogen Dioxide, 176 ppm LC50 (1 hour, estimated); 88 ppm LC50 (4 hour), rat
Phosgene (COCl2), 5 ppm LC50 (1 hour), animal species not identified; 2.5 ppm LC50
(4 hour, estimated), rat
Phosphine (PH3), 22 ppm LC50 (1 hour, estimated), rat; 11 ppm LC50 (4 hour), rat
Selenium Hexafluoride, 50 ppm LC50 (1 hour), animal species not identified; 25 ppm
LC50 (4 hour, estimated)
Stibine (SbH3), 20 ppm LC50 (1 hour), animal species not identified; 10 ppm LC50
(4 hour, estimated)
Tellurium Hexafluoride, 10 ppm LCLo (1 hour, estimated), rat; 5 ppm LCLo (4 hour), rat
III. Acutely Toxic Vapors (LC50 or LCLo ≤ 0.5 mg/L)
Example Chemicals - list not all inclusive:
Acrolein, 0.018 mg/L (7.9 ppm) LC50, 4 hours, rat
1,3-Butadiene Diepoxide, 0.32 mg/L (90 ppm) LC50, 4 hours, rat
Dimethyl Sulfate, 0.045 mg/L (8.7 ppm) LC50, 1 hour, rat
Iron Pentacarbonyl, 0.08 mg/L (10 ppm) LC50, 4 hours, rat
Methyl Chloroformate, 0.34 mg/L (88 ppm) LC50, 4 hours, rat
Methylhydrazine, 0.06 mg/L (34 ppm) LC50, 4 hours, rat
Methyl Isocyanate, 0.14 mg/L (6.1 ppm) LC50, 6 hours, rat
Nickel Carbonyl, 0.25 mg/L (35 ppm) LC50, 30 min., rat
Nitric Acid, red fuming (HNO3 >90%; NO2 >6%), 0.17 mg/L (67 ppm) LC50, 4 hours, rat
Osmium Tetroxide, 0.42 mg/L (40 ppm) LCLo, 4 hours, rat
Phenyl Isocyanate, 0.022 mg/L (4.5 ppm) LC50, 4 hours, rat
Phosphorus Oxychloride, 0.20 mg/L (32 ppm) LC50, 4 hours, rat
Tetranitromethane, 0.14 mg/L (18 ppm) LC50, 4 hours, rat
Thiophosphoryl Chloride (stench), 0.14 mg/L (20 ppm) LC50, 4 hours, rat
Extremely Reactive Chemicals
- Explosive Chemicals
Synthesis of any explosive chemical, or any reaction involving an explosive chemical.
- Pyrophoric Chemicals
Examples of substances considered to be pyrophoric (not all inclusive):
Alane (AlH3)
Bis(3,5-dimethylphenyl)phosphine
1,2-Bis(phosphino)benzene
1,2-Bis(phosphino)ethane
n-Butyllithium
sec-Butyllithium
tert-Butyllithium
Cadmium dust (not granules, pieces, or shot)
Cyclohexylphosphine
Di- tert-butylphosphine
Dicyclohexylphosphine
Dicyclopentylphosphine
Diethylphosphine
Diethylzinc
Diisobutylphosphine
Diisopropylphosphine
Dimethylcadmium
Dimethylchlorophosphine
Dimethylzinc
Di-2-norbornylphosphine
Diphenylphosphine
Di- p-tolylphosphine
Germane (germanium tetrahydride)
Hafnium powder (not crystal bar chips, foil, or wire)
Phenylphosphine
Phosphine
Phosphorus (white)
Silane
Sodium potassium alloy
Sodium tetraethylborate
Triethylphosphine
Triethylaluminum
Triethylgallium
Triethylboron
Triisobutylaluminum
Trimethylaluminum
Trimethylantimony
Trimethylboron
Trimethylgallium
Trimethylindium
2,4,4-Trimethylpentylphosphine
Appendix II: Standard Operating Procedure Template
The following template shows the information required in a Standard Operating Procedure. Contact EH&S for a printable template form.
- Chemical, chemical class, or procedure
- Revision date
- Prepared by
- Lab supervisor
- Location
- Hazards
- Engineering controls (for example, chemical fume hood or other ventilation device)
- Safe work procedures/designated area
- Personal protective equipment
- Safety equipment
- Transport and storage
- Chemical disposal
- Standard accumulation and disposal through EH&S department
- Additional accumulation or disposal procedures (describe)
- Incident response
- Standard response procedures as described in the UNR Chemical Hygiene Plan
- Additional incident response procedures (describe)
- Experimental procedure(s) (indicate if attached)
- Prior approval: Is prior approval by laboratory supervisor required before performing this procedure? Yes/No
- Approval signature of Laboratory Supervisor and date