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Managing Particularly Hazardous Substances in your Laboratory

See also the Managing Chemical Retention and Storage in your Laboratory and Peroxide Forming Chemicals factsheets.

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INTRODUCTION

Before beginning laboratory research with a particular substance, the hazard properties of that substance should be known in order to determine appropriate personal protection and safe handling procedures. The Material Safety Data Sheet (MSDS) is a good source of hazard information for most substances.

Certain substances are considered to be "Particularly Hazardous Substances" (PHS) by the Occupational Safety and Health Administration (OSHA) due to their potential to cause severe adverse health effects. Particularly Hazardous Substances should be identified, evaluated, and managed in accordance with this guidance document to ensure that adequate protection is provided.

IDENTIFICATION OF A PARTICULARLY HAZARDOUS SUBSTANCE

The OSHA Laboratory Standard (29 CFR 1910.1450) defines a Particularly Hazardous Substance as a select carcinogen, reproductive toxin, or substance with a high degree of acute toxicity.

• Select carcinogens are those that are listed by OSHA, the International Agency for Research on Cancer (IARC), and the National Toxicology Program (NTP) as known or suspected human carcinogens. Complete lists of these compounds can be found online at
  OSHA, the NTP Annual Report on human carcinogens, and the IARC Monographs on human carcinogens.
• Reproductive toxins are chemicals that may adversely affect male and female reproductive health and the developing fetus. One source of information about reproductive toxins is the Proposition 65 list developed by the State of California. This list is updated annually and available online.
• Chemicals having high acute toxicity are those that have oral, inhalation, or dermal LD₅₀ and LC₅₀ values below specified thresholds listed in the OSHA Lab Standard. These values are as follows:
  

  Oral LD50 (albino rats)	< 50 mg/kg
  Dermal LD50 (albino rabbits)	< 200 mg/kg
  Inhalation LC50 (albino rats)	< 200 ppm in air
  Probable Equivalent Lethal Oral Dose in Humans (70 kg)	< 3.5 g (@ 1/10 oz. or 1/2 teaspoon)

Select Toxins

As a result of requirements of the U.S. Department of Health and Human Services (DHHS) and the U.S. Department of Agriculture (USDA), a select group of biologically-derived toxins have been identified that are considered particularly hazardous because of their acute toxicity. Extreme care should be taken when working with any of these materials. Specific regulations apply when any investigator or laboratory possesses amounts above the regulatory threshold level. These agents and threshold quantity levels are provided in the tables below.*

*For more information on Biotoxins - Please check the following link on the VEHS website at http://www.safety.vanderbilt.edu/resources/biosafety_guidelines.htm.

PROCEDURES TO FOLLOW WITH PHS:

• Maintain a current inventory of PHS in your laboratory - Have this available for all lab employees and kept up to date. Chemtracker is available for use at Vanderbilt University to assist with maintaining inventories. Staff and students should be trained on the hazards of the PHS in the laboratory.
• The smallest possible chemical container or gas cylinder should be used for the experiment. A well-managed research plan will reduce the potential for exposure to PHS by limiting the quantity of material to the minimum required.
• Establish Designated Work Areas for Use of PHS - Determining a designated work area depends on the circumstances of use of the PHS. A designated area may be a specific area of the lab, or a device such as a hood or glove box. There may be dedicated equipment for use with PHS.
• Make PHS clearly visible to laboratory workers. Highly visible colored containers or labels can be used to mark PHS. Designated areas or equipment can be marked with signs reading "DESIGNATED AREA FOR USE OF PARTICULARLY HAZARDOUS SUBSTANCES - AUTHORIZED PERSONNEL ONLY".
• Avoid inhalation of PHS. Take action to prevent skin contact. Use appropriate personal protective equipment such as chemical resistant gloves, safety glasses, and protective clothing as necessary. Respiratory protection may be necessary where materials are handled outside chemical fume hoods or glove boxes and exposure limits may be exceeded. Contact VEHS regarding any use of respiratory protection.
• Thoroughly decontaminate and clean designated areas at regular intervals. This may be as simple as a wiping a counter with a wet paper towel or periodic use of a neutralizing agent. Proper decontamination procedures are determined by the type of chemical, the amount of use, the location of use and other factors.
• Be prepared for accidents. Secondary containment for chemical containers is recommended. Keep spill control materials on hand and establish a plan for responding to spills including a determination when to call for outside help, an evacuation plan, and any special treatment materials needed (such as calcium gluconate gel).
• Highly toxic gas cylinders must be enclosed in gas cabinets with the following features:
  • Self-closing limited access ports or fire-rated windows
  • Self-closing doors
  • Negative pressurization inside the cabinet relative to the surrounding area
  • Face velocities on access ports greater than 200 feet per minute
  • At least 12-gauge steel construction
  • Treatment systems connected to the exhaust
• A continuous gas monitoring system must be available for highly toxic gases. Sensing ports should be located in the gas cabinets, in the equipment (where the delivery gas line terminates) and in the lab operator area.

Commonly Used Particularly Hazardous Substances (Chemicals) at Vanderbilt University (list not inclusive):

acetaldehyde
acrolein
acrylamide
acrylonitrile
ammonia (anhydrous)
ammonium hydroxide
aniline
arsenic
arsenic pentoxide
arsenous oxide
benzene
benzenearsonic acid
beryllium
boron tribromide
bromine
brucine
butyl lithium
cadmium
cadmium bromide
cadmium chloride
cadmium oxide
carbon disulfide
carbon tetrachloride
chloroacetic acid
chloroform
chloromethyl ether
chloromethyl ether
chlorotrimethylsilane
chromium hexacarbonyl
chromium trioxide (& other Cr VI salts)
cobalt carbonyl
cyanogen bromide
diazomethane
dichloromethane
diethylnitrosamine
dimethyl mercury
dimethyl sulfate
dimethylaniline
dioxane
ethidium bromide
ethylene diamine
ethylene dibromide
ethylene oxide
fluoroacetyl chloride
formaldehyde
formamide
glutaraldehyde
hexamethylphosphoramide
hydrazine hydrate
hydrochloric acid
hydrofluoric acid
hydrogen peroxide
iodine
lead and its inorganic compounds
(excluding shielding materials)
manganese chloride
mercuric chloride
mercuric oxide
methyl iodide
methyl mercury
methyl vinyl ketone
nickel carbonyl
nickel chloride
nickel nitrate
nitrobenzene
nitrogen dioxide
osmium tetroxide
palladium on carbon
paraformaldehyde
peracetic acid
phenol
phosphorus
phosphorus pentoxide
picric acid
potassium hydroxide
potassium cyanide
propargyl bromide
silane
sodium azide (Na (N3))
sodium cyanide (Na (CN))
sodium hydroxide
sulfur dioxide
sulfur trioxide
tert butyl hydroperoxide
tetrafluoroboric acid
tetramethyl ethylenediamine
thallium compounds
toluene
toluene diisocyanate (mixture of isomers)
toluene diisocyanate
trichloroethylene
triethylamine
trifluoroacetic acid
trimethyltin chloride

Common Used Particularly Hazardous Substances (Gases) at Vanderbilt University (list not inclusive):

arsine
boron trifluoride
carbon monoxide
chlorine
diborane
dichlorosilane
fluorine
hydrogen chloride
hydrogen cyanide 
hydrogen fluoride
hydrogen selenide
hydrogen sulfide
nitrogen dioxide
nitric oxide
ozone
phosgene
phosphine

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