CHEMICAL HAZARD ASSESSMENTS

Hazard assessments are conducted to identify the hazards and necessary controls for chemicals used in shop and laboratory work environments. These are performed so that protective measures can be put into place and to assure that the proper level of work authorization is obtained.  In accordance with Integrated Safety Management (ISM) principles, line managers are responsible for "integrating ES&H into work and for ensuring active communication up and down the management line with the workforce".  To this end, line managers must be aware of and approve the work performed under their jurisdiction and shall ensure that appropriate hazard assessments are conducted in their work areas.  An industrial hygienist may be consulted to provide assistance and guidance in performing hazard assessments.

Activity Hazard Documents

The LBNL protocol for determining the proper level of work authorization is delineated in Pub 3000 Chapter 6, EH&S Documentations and Approvals.

An AHD is a work authorization that identifies hazards and describes how they are controlled. It is the Laboratory document used to describe the controls necessary to ensure that the risks associated with an activity are at an acceptable level. The line manager must identify and evaluate all potential hazards associated with a proposed project or activity and develop measures to reduce these hazards to an acceptable level.  The line manager must also determine whether an AHD is needed. The AHD is required to be completed before work is inititated. When reviewed and approved, the AHD becomes the principal safety document for the research project or activity. The ultimate determination of the appropriate work authorization is the responsibility of the leader of that work (Principal Investigator, manager or supervisor). The AHD is reviewed by EH&S health and safety professionals and line management. It is jointly approved by the using Division Director and EH&S.

Examples of work requiring AHDs include:

• Activities requiring the use of glove boxes for safety reasons
• Activities using toxic and/or pyrophoric gases. The following list provides examples of these gases.  (Pub 3000 Chapter 13, Gases, may be consulted for further guidance for toxic and pyrophoric gases controls). This list is not all inclusive. An MSDS should be consulted to determine if the material is a toxic or pyrophoric gas.

1,3 butadiene	iodine pentafluoride
ammonia	methyl bromide
arsenic pentafluoride	methyl chloride
arsine	methyl silane
boron trichloride	nickel carbonyl
boron trifluoride	nitric oxide
bromine pentafluoride	nitrogen dioxide
bromine trifluoride	nitrogen trifluoride
carbon monoxide	nitrosyl chloride
carbonyl fluoride	oxygen difluoride
carbonyl sulfide	phosgene
chlorine	phosphine
chlorine trifluoride	phosphorus pentafluoride
cyanogen	phosphorus trichloride
cyanogen chloride	phosphorus trifluoride
diborane	selenium hexafluoride
dichlorosilane	silane
fluorine	silicon tetrafluoride
germane	stibine
hydrogen bromide	sulfur dioxide
hydrogen chloride	sulfur tetrafluoride
hydrogen cyanide	sulfuryl fluoride
hydrogen fluoride	tellurium hexafluoride
hydrogen selenide	tungsten hexafluoride
hydrogen sulfide	vinyl chloride

• Use of extremely reactive and/or explosive substances. The following list provides examples of these materials, but is not all inclusive. Therefore, an MSDS should be consulted to determine if the material is reactive or explosive.

• Other chemicals that are known to posses lethal or incapacitating toxicity shall also require an AHD.  These include materials with an LD₅₀ of 0.5 mg/kg or less. An MSDS should be consulted to determine if a material is acutely toxic.

Chemical Name [CAS#]

Amiton: O,O-Diethyl S-[2-(diethylamino)ethyl] phosphorothiolate and corresponding alkylated or protonated salts (78-53-5)

O-Alkyl (<C10, incl. cycloalkyl) alkyl (Me, Et, n-Pr or i-Pr)-phosphonofluoridates Sarin: O-Isopropyl methylphosphonofluoridate (107-44-8) Soman: O-Pinacolyl methylphosphonofluoridate (96-64-0)

O-Alkyl (<C10, incl. cycloalkyl) N,N-dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidocyanidates Tabun: O-Ethyl N,N-dimethyl phosphoramidocyanidate (77-81-6)

O-Alkyl (H or <C10, incl. cycloalkyl) S-2-dialkyl(Me, Et, n-Pr or i-Pr)-aminoethyl alkyl(Me, Et, n-Pr or i-Pr) phosphonothiolates and corresponding alkylated or protonated salts VX: O-Ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate [50782-69-9]

Sulfur mustards: 2-Chloroethylchloromethylsulfide [2625-76-5] Mustard gas: Bis(2-chloroethyl)sulfide [505-60-2] Bis(2-chloroethylthio)methane [63869-13-6] Sesquimustard: 1,2-Bis(2-chloroethylthio)ethane [3563-36-8] 1,3-Bis(2-chloroethylthio)-n-propane [63905-10-2] 1,4-Bis(2-chloroethylthio)-n-butane [142868-93-7] 1,5-Bis(2-chloroethylthio)-n-pentane [142868-94-8] Bis(2-chloroethylthiomethyl)ether [63918-90-1] O-Mustard: Bis(2-chloroethylthioethyl)ether [63918-89-8]

Lewisites: Lewisite 1: 2-Chlorovinyldichloroarsine [541-25-3] Lewisite 2: Bis(2-chlorovinyl)chloroarsine [40334-69-8] Lewisite 3: Tris(2-chlorovinyl)arsine [40334-70-1]

Nitrogen mustards: HN1: Bis(2-chloroethyl)ethylamine [538-07-8] HN2: Bis(2-chloroethyl)methylamine [51-75-2] HN3: Tris(2-chloroethyl)amine [555-77-1]

Saxitoxin [35523-89-8]

Ricin [9009-86-3]

Alkyl (Me, Et, n-Pr or i-Pr) phosphonyldifluorides DF: Methylphosphonyldifluoride [676-99-3]

O-Alkyl (H or <C10, incl. cycloalkyl) O-2-dialkyl(Me, Et, n-Pr or i-Pr)-aminoethyl alkyl(Me, Et, n-Pr or i-Pr) phosphonites and corresponding alkylated or protonated salts QL: O-Ethyl O-2-diisopropylaminoethyl methylphosphonite [57856-11-8]

Chlorosarin: O-Isopropyl methylphosphonochloridate [1445-76-7]

Chlorosoman: O-Pinacolyl methylphosphonochloridate [7040-57-5]

PFIB: 1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene [382-21-8]

BZ: 3-Quinuclidinyl benzilate (*) [6581-06-2]

Chemicals containing a phosphorus atom to which is bonded onemethyl, ethyl or propyl (normal or iso) group but not further carbon atoms Methylphosphonyl dichloride [676-97-1] Dimethyl methylphosphonate [756-79-6] Exemption: Fonofos: O-Ethyl S-phenyl ethylphosphonothiolothionate [944-22-9]

N,N-Dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidic dihalides

Dialkyl (Me, Et, n-Pr or i-Pr) N,N-dialkyl(Me, Et, n-Pr or i-Pr)-phosphoramidates

Arsenic trichloride [7784-34-1]

2,2-Diphenyl-2-hydroxyacetic acid [76-93-7]

Quinuclidin-3-ol [1619-34-7]

N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethyl-2-chlorides and corresponding protonated salts

N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols and corresponding protonated salts Exemptions: N,N-Dimethylaminoethanol and corresponding protonated salts [108-01-0] N,N-Diethylaminoethanol and corresponding protonated salts [100-37-8]

N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-thiols and corresponding protonated salts

Thiodiglycol: Bis(2-hydroxyethyl)sulfide [111-48-8]

Pinacolyl alcohol: 3,3-Dimethylbutan-2-ol [464-07-3]

The following chemicals also exhibit toxic properties of great concern.  An EH&S Industrial Hygienist should be consulted prior to purchase and use of these chemicals to determine if an AHD is required:

Chemical Name [CAS#]

Phosgene: Carbonyl dichloride [75-44-5]

Cyanogen chloride [506-77-4]

Hydrogen cyanide [74-90-8]

Chloropicrin: Trichloronitromethane [76-06-2]

Phosphorus oxychloride [10025-87-3]

Phosphorus trichloride [7719-12-2]

Phosphorus pentachloride [10026-13-8]

Trimethyl phosphite [121-45-9]

Triethyl phosphite [122-52-1]

Dimethyl phosphite [868-85-9]

Diethyl phosphite [762-04-9]

Sulfur monochloride [10025-67-9]

Sulfur dichloride [10545-99-0]

Thionyl chloride [7719-09-7]

Ethyldiethanolamine [139-87-7]

Methyldiethanolamine [105-59-9]

Triethanolamine [102-71-6]

If there is any uncertainty regarding the need to develop an AHD, the line manager must contact an EH&S Industrial Hygienist for guidance.

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