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CHEMICAL HAZARD ASSESSMENTS

Hazard assessments are conducted to identify the hazards and necessary controls for chemicals used in shop, field, and laboratory work environments. These preliminary evaluations are part of the Job Hazards Analysis (JHA) process and can be performed by the Line Manager, Work Lead, Supervisor, or an EH&S professional.  Hazard assessments may precede Exposure Assessments which are conducted by EH&S professionals to ensure that protective measures are implemented and to ensure that the proper level of work authorization is obtained.   Exposure Assessments are required prior to issuing or using respiratory protection equipment. For more information on Hazard and Exposure Assessments, refer to PUB-3000, Chapter 32, Appendix E, Exposure Assessments.

In accordance with Integrated Safety Management (ISM) principles, Work Leads 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, they must be aware of and authorize the work performed under their jurisdiction and should ensure that appropriate Hazard Assessments and Exposure Assessments, as necessary, are conducted in their work areas.

All work performed at LBNL must be authorized by Safety Line Management. The LBNL protocol for determining the proper level of work authorization is delineated in PUB-3000, Chapter 6, “Safe Work Authorizations.” The ultimate determination of the appropriate work authorization is the responsibility of the PI or the supervisor for that work.

Job Hazards Analysis (JHA)

A Job Hazards Analysis (JHA) is the overall work-authorization document that analyzes the tasks that a worker performs, the hazards associated with those tasks, and the controls necessary to perform the work safely. The Job Hazards Analysis process is given in PUB-3000, Chapter 32, “Job Hazards Analysis.” All work at LBNL must be authorized through the JHA. Work may not be performed until the Job Hazards Analysis is complete, the work is authorized by the Work Lead, and the proper controls as specified by the JHA are in place.

As part of the process of determining the proper controls for a task, it may be necessary to conduct exposure assessments. An exposure assessment is a formal evaluation process performed and documented by EH&S professionals to determine the risk of personnel exposure to hazardous chemical, biological, or physical agents, and the adequacy of hazard controls. Results of exposure assessments are used to: assure proper employee health protection, validate or improve hazard controls, extend the same controls to employees performing similar work, provide employees with appropriate medical tests and examinations (i.e., medical surveillance), monitor employee health, and demonstrate compliance with regulations.

Activity Hazard Document

OSHA mandates employers to identify higher hazard work that requires prior approval.  At LBNL this is accomplished with the  Activity Hazard Document (AHD).  An AHD is a formal work authorization which lists controls and procedures to reduce the risks associated with a higher-hazard activity to an acceptable level. AHDs are incorporated into the Job Hazards Analysis by reference. The PI /Supervisor 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.  He/she must also determine whether an AHD is needed. The AHD is required to be completed before work is initiated. When reviewed and approved, the AHD becomes the principal safety document for that higher-hazard portion of the research project or activity. The AHD is reviewed by EH&S health and safety professionals and line management. Work under an AHD is authorized by the responsible Division Director with EH&S concurrence.

The LBNL protocol for determining the proper level of work authorization is delineated in PUB-3000, Chapter 6, “Safe Work Authorizations.”  

All AHDs are developed, reviewed, and approved through the Laboratory’s Activity Hazard Document Database.

Examples of activities requiring AHDs include:

  • Activities requiring the use of gloveboxes for safety reasons
  • Work that uses toxic or pyrophoric gases.  (PUB-3000, Chapter 13, “Gases,” may be consulted for further guidance regarding controls for toxic and pyrophoric gases).
  • Activities that involve reactive or explosive chemicals.
  • Work that uses chemicals possessing lethal or incapacitating toxicity or chemicals that have an LD50 of 0.5 mg/Kg or less.
  • Other activities with chemicals for which an EH&S Industrial Hygienist determines that an AHD is required.

Below are several lists of chemicals that correspond to these work activities.  Note these lists are NOT inclusive. Consult sources such as Material Safety Data Sheets (MSDSs) must be consulted to determine hazardous properties of chemicals:

Toxic/Pyrophoric Gases:

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

Reactive and Explosive Substances:

aluminum hydride picric acid
benzoyl peroxide Potassium
cesium rubidium
copper azide sodium
lead azide sodium azide
lithium triethyl aluminum
phosphorus (white) trimethyl aluminum


Chemicals possessing lethal or incapacitating toxicity 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 one methyl, ethyl, or propyl (normal or iso) group but no 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 concern.  An EH&S Industrial Hygienist must 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]
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 for work involving chemicals, the Work Lead must contact an EH&S Industrial Hygienist for guidance.

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Last updated: 12/18/2008
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