SPECIAL PROVISIONS FOR SELECT CARCINOGENS, REPRODUCTIVE TOXINS AND ACUTELY TOXIC CHEMICALS

 

The Lab Standard (1910.1450(e)(3)(viii)) requires additional employee protection when working with particularly hazardous substances. UK has developed a Standard Operating Procedure (SOP) template to document the required provisions. "Select Carcinogens," (see Appendix VII for a list of select carcinogens) reproductive toxins, engineered nanomaterials and substances which have a high degree of acute toxicity meet the requirements for an SOP. If the SDS of the chemical/mixture of interest meets one of the criteria, pictograms, GHS class, and/or category listed below in an SOP must be developed for that chemical. If the SDS does not contain information specific to the desired concentration to be used, an SOP is required for mixtures of >10%. If acute toxicity information (ATE) is unavailable, the chemical or mixture should be assumed highly toxic and an SOP must be developed. The following provisions must be included in an SOP before work begins:

 

1.        Establishment of a designated area

2.         Use of containment devices such as chemical fume hoods or glove boxes

3.        Procedures for safe removal of contaminated waste; and

4.        Decontamination procedures.

 

Criteria	Pictogram	GHS (Class, Hazard Category, Route)
Carcinogen		Carcinogenicity, Category 1A or 1B
Reproductive toxicant	Reproductive Toxicity, Category 1A or 1B
Mutagen	Category 1A or 1B)
Respiratory sensitizer	Respiratory Sensitization, Category 1A
Highly acute toxicant		Acute toxicity, Category 1 or 2, Inhalation or Dermal Acute toxicity, Category 1, Oral Specific Target Organ Toxicity - Single Exposure, Category 1 Skin Sensitizer, Category 1A
Corrosive
Skin/Eye Corrosion Category 1(A,B,C) Corrosive to metals Category 1
Reactive		Oxidizing Liquids, Category 1 Oxidizing Solids, Category 1
Explosive/Unstable		Explosives, Divisions 1.1, 1.2 or 1.3 Unstable explosive Organic peroxides Type A and B Desensitized explosives Category 1 or 2 Self Reactives Type A and B
Flammable		Flammable gas Category 1A Pyrophoric gas Chemically unstable gas Pyrophoric Liquid Category 1 Pyrophoric solid Water Reactives Category 1 or 2 Self Reactives Type C – F Self-heating substances, Category 1
		In contact with water liberates toxic gas

*This information is taken from The United Nations Economic Commission for Europe (UNECE) Globally Harmonized System for Classification and Labeling (GHS).

 

In addition to the general safety guidelines mentioned in the first section and throughout the CHP, special precautions are needed when handling mutagens, carcinogens, reproductive toxins, and chemicals with a high degree of acute toxicity.  A minimum set of guidelines that should be followed is listed below. The lab supervisor should ensure that these and other precautions designed to minimize the risk of exposure are taken.

 

           Quantities of these chemicals used and stored in the laboratory must be minimized, as should their concentrations in solution or mixtures.

 

           Work with mutagens, carcinogens, reproductive toxins and acutely toxic chemicals must be performed within a certified functioning chemical fume hood, biological safety cabinet, ventilated glove box, sealed system, or other system designed to minimize exposure to these substances. (The exhaust air from the ventilation systems may require scrubbing, or other treatment, before being released into the atmosphere.) In all cases, work with these types of chemicals must be done in such a manner that the OSHA permissible exposure limits (PELs) or similar standards are not exceeded.

 

• Certain chemicals are known or suspected to harm fetuses or the reproductive health of adults. Some examples of reproductive toxins are: anesthetic gases, arsenic and certain arsenic compounds, benzene, cadmium and certain cadmium compounds, carbon disulfide, ethylene glycol monomethyl and ethyl ethers, ethylene oxide, lead compounds, mercury compounds, toluene, vinyl chloride, xylene, and formamide. The first trimester of pregnancy is a period of high susceptibility. Often a woman does not know that she is pregnant during this period. Individuals of childbearing potential are warned to be especially cautious when working with such reproductive toxins. These individuals must use appropriate protective apparel (especially gloves) to prevent skin contact.

 

• Pregnant women and women intending to become pregnant should seek advice from knowledgeable sources before working with substances that are suspected to be reproductive toxins. These sources include the Laboratory Supervisor, Safety Data Sheets, the UK Environmental Health and Safety office. Notify supervisors of all incidents of exposure or spills; consult a qualified physician when appropriate.

 

           Compressed gas cylinders that contain acutely toxic chemicals such as arsine, chlorine, and nitrogen dioxide must be kept in well-ventilated areas.

 

           The ventilation efficiency of the designated laboratory chemical hood, glove box or gas cabinet and the operational effectiveness of mechanical and electrical equipment used to contain or manipulate these special substances should be evaluated periodically by the laboratory personnel at intervals determined by the Laboratory Supervisor.  The interval of evaluating systems may vary from weekly to annually depending upon the frequency of usage, quantities employed and level of hazard.

 

           Each laboratory utilizing these substances must designate an area for this purpose and must sign or mark this area with an appropriate hazard warning.  The designated area may be an entire laboratory (bio-safety level three or four require that the ENTIRE laboratory be designated), an area of the laboratory or a device such as a Laboratory chemical hood or glove box.  The designated area should be marked with a DANGER, specific agent, AUTHORIZED PERSONNEL ONLY or comparable warning sign.

 

           All laboratory workers who work in a laboratory which has an area designated for use with mutagens, carcinogens, reproductive toxins and acutely toxic chemicals must be trained about the deleterious effects of these substances as well as signs and symptoms of exposure, whether or not they actually work with the substance themselves.  Training to ensure the safe handling and storage of these substances is required for those who use these materials.  This training is the responsibility of the Laboratory Supervisor and must be done prior to the use of any of these materials.

 

           Laboratory Workers working with these chemicals must have access to appropriate protective equipment and clothing (available at no expense to the workers) and must be trained on how to properly utilize the safety equipment.  For example, when working with highly toxic gases, it is often recommended that the workers be trained by Environmental Management to use a self-contained breathing apparatus.

 

           Detection equipment may be required in laboratories where chemicals (especially poisonous gases) with a high degree of acute toxicity are utilized.

 

           For special disposal information, call Environmental Management (323-6280).

 

           The designated working area must be thoroughly and appropriately decontaminated and cleaned at regular intervals determined by the Laboratory Supervisor.  The interval may be as short as one day or as long as six months depending upon the frequency of usage and level of hazard.

 

           Special precautions to avoid release and exposure of highly toxic chemicals, mutagens, carcinogens, and reproductive toxins must be utilized.  For instance, volatile substances should be kept cool and contained.  Gases should have properly functioning valves, check valves, regulators, containment that can withstand pressure buildup, and appropriate piping.  Dispersive solids should be kept in closed containers, used in places with minimum air currents, and appropriate contact materials should be used to avoid static charging.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

SAFETY INVOLVING ENGINEERED NANOMATERIALS

Auditing

UK Occupational Health and Safety (OHS) is collecting data on engineered nanomaterial. A database with material, procedure, and exposure information has been developed. This list is an attempt to consolidate and profile engineered nanomaterials in use at UK. 

Nanomaterials are natural, incidental or manufactured materials containing particles, in an unbound state, as an aggregate, or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions ranges in size from 1nm-100nm.

Hazard Assessment

UK OHS will perform a hazard assessment on all operations identified as having engineered nanomaterials. Written procedures will be used, and operations will be monitored for airborne emissions. A TSI Ultrafine Particle Counter will be utilized to demonstrate containment or potential point source emissions. In all cases, a specific exposure control plan for the work will be developed and followed in the lab.

Exposure Control Plan

UK has developed guidelines for research involving nanomaterials. These guidelines closely follow NIOSH’s suggested exposure control procedures.

Controlling exposures for nanomaterials is much the same as for any particulate. Since the toxicological data are somewhat limited, controls may be more stringent than they would be for a similar material in the non-nano size range. The following is a general description of what considerations will be made for processes and lab specific plans. 

1. Engineering Controls - the first line of defense in protection from exposures.
   1. Closed systems – A closed system is one in which pipes, glassware, and chambers seal the material from the user.
   2. Fume Hoods -The most common type of engineering control to be utilized at UK will be fume hoods. In general, UK labs performing research utilizing engineered nanomaterials in solid/powder form will be performed in designated fume hoods. Fume hoods will also be used for processes that have the potential to aerosolize engineered nanomaterials that are in solution. 
   3. Clean Benches or Laminar Flow Hoods - Some processes and labs will utilize clean bench systems that are equipped with HEPA filtered air to provide both product and worker protection. Hoods that do not provide worker protections will not be used when manipulating dry/powder engineered nanomaterials.
   4. Each process will be evaluated, and employee exposure monitoring performed to ensure the utilized engineering controls are effectively capturing the materials.
2. Work Practices - SOPs for work involving nanomaterials are required.  SOPs will be reviewed by OHS and/or the Chemical Safety Committee.
   1. Wet methods for the manufacture or fabrication of nanomaterials are preferred.  This will decrease the probability of inhalation exposures by reducing airborne particles.  Processes that utilize other techniques will be evaluated on an individual basis and work practices developed.
   2. All operations will take place in a designated area.  Labs approved for this work have at least a fume hood, hand washing facilities, and emergency shower and eyewash stations. All labs and lab workers are required to follow the UK Chemical Hygiene Plan.  In this document, all lab workers are required to dress appropriately, not store consumables in the lab, not eat, drink, smoke, apply makeup or lip balm in the lab, and to wash hands before leaving the lab.
   3. Additional templates for Material Specific and Operations Specific SOPs can be found at the following website: GoodNanoGuide
3. Personal Protective Clothing- Standard laboratory protective equipment will be worn which includes: lab coat, safety glasses and closed toed shoes. 
   1. Gloves shall be worn when handling engineered nanomaterials. Selection shall be based on available data. Current testing of glove materials can include particles in the nano size range, i.e. viruses. Ensure gloves have been tested by the manufacture for protection against nanomaterials. When nanomaterials are in suspension, the solvent will dictate the glove material. General compatible glove material information can be found in the UK Chemical Hygiene Plan (CHP) or for assistance on glove material compatibility contact the specific glove manufacturer or contact UK Occupational Health and Safety (OHS) at 7-3827.
   2. Respirators - In general, respiratory protection should not be required for work with engineered nanomaterials.  OHS will evaluate operations to determine if available engineering controls are not adequate and will assign appropriate respirators.  Affected individuals will be enrolled in lab specific respiratory protection programs that will require fit testing and training.
4.  Clean-up and disposal - Standard techniques will be used to clean up spills and disposal of nanomaterials.  Refer to UK Hazardous Waste Manual for specific information of call 3-6280.
   1. Dry material spills outside of the fume hood or clean bench will be considered a hazardous materials spill. If lab personnel are not part of a respiratory protection program, then the SOP will indicate that the lab will be cleared and secured.  Environmental Management (EM) will be contacted to clean.  EM employees have the PPE and training required for cleaning spills in the lab.
   2. Liquid spills will be evaluated based on the solvent the materials are suspended in. Due to typical research quantities needed in a lab, it is not anticipated that these spills will be large.  Small spills will be handled by lab personnel following lab specific SOPs that have been developed. Particularly hazardous solvent spills will be identified in the lab SOP and the appropriate course of action will be described.
   3.  Disposal- Nanomaterials in themselves do not constitute a hazardous waste. All local, state, and federal regulation must be followed for wastes that meet certain criteria. Prior to working with engineered nanomaterials, the appropriate waste stream will be determined and written in the specific SOP.
5. Medical Surveillance - Engineered nanomaterials that contain materials regulated by current OSHA standards will be subject to the requirements of those standards. NIOSH is currently working on recommendations as to when medical surveillance should be implemented for workers potentially exposed to nanomaterials, regulated, and not otherwise regulated.
   1. The need for medical surveillance for nanomaterials that are not otherwise regulated will be assessed on an individual project/operation basis.  A risk-based approach will be taken using such factors as route of entry, available toxicological data, engineering and work practice controls, duration of activity, and results of exposure monitoring.  The medical surveillance will be a cooperation between the laboratory worker, the Principal Investigator of the laboratory, Occupational Health and Safety, as well as a medical provider if needed.  
   2. OSHA regulated material - Medical surveillance may be required for research involving these hazardous materials. A review of the requirement will be done for each nanomaterial utilized and a determination made.
      1. Asbestos
      2. Coal tar pitch volatiles
      3. 13 listed OSHA carcinogens (29 CFR1910.1003)
      4. alpha-Naphthylamine
      5. Methyl chloromethyl ether
      6. beta-Naphthylamine
      7. Benzidine
      8. 4-aminodiphenyl
      9. Ethyleneimine
      10. beta-propiolactone
      11. 2-Acetylaminafluorene
      12. 4-Dimethlyaminoazobenzene
      13. N-Nitrosodimethylamine
      14. Vinyl chloride
      15. Inorganic arsenic
      16. Lead
      17. Chromium (VI)
      18. Cadmium
      19. Coke oven emissions
      20. Bloodborne Pathogens
      21. Cotton dust
      22. 1,2-Dibromo-3-chloropropane
      23. Acrylonitrile
      24. Ethylene oxide
      25. Formaldehyde
      26. Methylenedianiline
      27. 1,3-Butadiene
      28. Methylene chloride
      29. Titanium Dioxide
      30. Carbon nanotubes and nanofibers

If this chapter is applicable to your lab, please include your lab specific information.