Hazardous chemical inventories are managed by following these steps:

• Identify and track hazardous chemicals. ChemTrack is the primary chemical tracking tool. See Section 3.5.1.
  
  
• Control quantities of hazardous chemicals. An important part of inventory control is determining when to dispose of hazardous chemicals, which can be done based on predetermined age, testing procedures, or upon observation of an unsatisfactory condition. See Section 3.5.2.
  
  
• Conduct reviews of hazardous chemicals in use and in storage areas periodically to ensure age and testing procedures are being fulfilled, and to identify cases where containers or their contents show evidence of deterioration. See Sections 3.5.3 and 3.5.4.

The authorizing organization is responsible for implementing these steps, except where specified in the text of this section. In addition, some chemicals can become hazardous with the passage of time, most notably chemicals that form peroxides. These are addressed in Sections 3.5.5 and 3.7.3. Legacy chemical concerns associated with the departure of workers or the decommissioning of a facility are addressed in Section 3.5.6.

3.5.1 Chemical Tracking and Inventory Management Functions

ChemTrack is the primary tool for tracking hazardous chemicals, although local inventory systems may be needed to address hazardous chemical use not captured by ChemTrack. To this end, chemical custodians shall:

• Ensure that ChemTrack bar code labels are on all primary and certain secondary containers (see Appendix A for the definition of a €œsecondary container€�) when required. Contact your ES&H Team for guidance on when to bar code label secondary containers.
  
  
• Update or notify ChemTrack (Ext. 4-4404) when obtaining either new chemicals or items to be entered into ChemTrack.
  
  
• Update or notify ChemTrack when disposing of bar coded chemical containers or transferring them to a non-LLNL location. This can be done by:
  
  
  • Accessing the ChemTrack Home Page and clicking on Update Inventory
    
    ������������������������������� http://chemtrack.llnl.gov/
    
    
  • Alternatively, remove the lower half of the bar code, affix it to a ChemTrack Disposal/Transfer Form, and mail the form to the ChemTrack Group (L-621).
    
    
• Comply with the facility€™s chemical inventory procedures.
  
  
• Working with facility management and RIs, ensure that hazardous chemical inventories are compiled and annually updated for both laboratory and nonlaboratory areas as part of the annual ChemTrack inventory and reconciliation process.
  
  
• Ensure that current, accurate information is entered into ChemTrack to facilitate informed decision making by the authorizing organization decisions concerning retaining, testing/treating, or disposing of stored chemicals per Section 3.5.5.

The ChemTrack Operations Group shall provide assistance with chemical inventories, and also maintains the Laboratory€™s MSDS database, the Chemical Safety databases, and ChemTrack/MSDS Hotline (extension 4-4404). ChemTrack responsibilities are defined in Document 21.1.

3.5.2 Controlling Quantities of Hazardous Chemicals

Authorizing organizations shall:

• Establish controls for hazardous chemical inventories based on quality control and program considerations.
  
  
• Manage chemical inventories and ensure that hazardous chemical inventories are limited to amounts needed to meet operational requirements. This shall be done by evaluating the:
  • Amount of a hazardous chemical in inventory,
  • Use,
  • Age (e.g., if older materials are in use or reasonably could be used, if the containers are deteriorating, or if other changes listed in Section 3.5.4 are evident), and
  • Safety or suitability of the chemicals for use.
    
    
• Ensure that hazardous chemicals are procured and stored consistent with program, ES&H, and waste minimization objectives (the LLNL Waste Minimization Program and how to minimize the quantities of chemicals in storage or use are described in Section 3.2.3).

Chemical custodians shall ensure that inventories of chemicals that are not being used (€œstockpiles€�) are reviewed annually to assess ongoing need (based on ES&H and/or quality control considerations). The chemical custodian or designee shall also evaluate the status of hazardous chemicals being stored (e.g., use, age, condition of storage container) on an ongoing basis to guide decisions about retaining or removing chemicals in an inventory.

3.5.3 Inspections

A visual periodic examination of stored hazardous chemicals is important for safety and decision making on continuing to store or dispose of chemicals. General requirements for evaluating hazardous chemical storage follow in this section.

Chemical Custodian Reviews. Chemical custodians shall ensure that their hazardous chemicals, including those on or in shelves and cabinets used to store chemicals, are periodically reviewed. A review frequency may be determined by the authorizing organization as appropriate. These reviews can be informal evaluations used to identify:

• Incompatible chemicals.
  
  
• Out-of-date chemicals.
  
  
• Chemicals no longer in use.
  
  
• Problem indicators listed in Section 3.5.4.

Hazards Control Department Inspections. The area ES&H Teams shall periodically check hazardous chemicals in accordance with Chemical/Biological Safety Discipline Action Plan Item 30, €œChemical Storage.€�

The chemical custodian and Hazards Control Department inspection activities can be coordinated.

3.5.4 Visible Changes Indicating a Chemical is Dangerous or Ready for Disposal

Some visible changes may indicate a chemical presents an imminent danger.

Contact the RI or, if the RI or other knowledgeable person is not available, call the Fire Department [dial 911, or, if using a cell phone or calling from offsite, dial 1 (925) 447-6880] if any of the following are found:

• Evidence of material peroxidization, such as
  • Exterior crystal growth.
  • Layering of liquids.
  • Discoloration.
    
    
• Bulging or overpressurization.
  
  
• Any other reaction that could potentially cause container handling to be extremely hazardous. This condition may have been observed, or an individual may have reason to believe it might have occurred.

These visible changes may indicate a chemical is ready for disposal:

• Slightly cloudy liquids.
  
  
• Change in chemical color.
  
  
• Spotting on solid chemicals.
  
  
• Caking of anhydrous chemicals (evidence of reaction with moisture).
  
  
• Presence of precipitates or particulates in liquids, or of liquid in solids.
  
  
• Container damage and age-related effects, such as
  • Signs of corrosion.
  • Cracking.
  • Changing shape or color.
  • Fading or deteriorating labels, labels falling off, or missing labels.
    
    
• Missing, deteriorating, or broken caps.

3.5.5 Stability of Hazardous Chemicals in Storage

Chemicals can become hazardous with the passage of time. At this time, the only groups of chemicals assessed for age-related hazards are the organic peroxides, peroxidizable compounds, explosives, and certain alkali metal compounds, although other chemicals exist that can become hazardous with the passage of time. Age limits have been set to minimize these hazards associated with peroxidizable chemicals (see Section 3.7.3). Age limits have also been set for toxic, corrosive, and reactive gases for a mixture of safety- and quality-related reasons.

Information on specific groups of materials that pose age-related hazards can be found in the ES&H Manual as follows:

• Storage and age limits of explosives: Documents 17.1, €œExplosives,€� and 17.2, €œLLNL Energetic Materials Stability Review Program.€�
  
  
• Age limits for toxic and reactive gases: Document 14.3, €œToxic, Corrosive, or Reactive Gases.€�
  
  
• Age-related hazards of peroxide and superoxide compounds of alkali metals: Document 14.7, €œSafe Handling of Alkali Metals and Their Reactive Compounds.€�

A list of specific peroxidizable chemicals can be obtained by going to the ChemTrack home page, clicking on the €œReports€� button to the left, then clicking on the ES&H button, logging in and then entering the type of report sought (e.g., €œLLNL peroxidizables€�).

For the chemicals described in this section, the chemical custodian shall ensure that:

• Those nearing the ends of their safety- or quality-based age limits are evaluated to determine if they are still useful and test them, if practical.
  
  
• Those at the end of their shelf lives, as evident by visible signs described in Section 3.5.4 or other means, are promptly sent off for disposal.

Chemical custodians, working with RIs, shall also ensure that chemicals are periodically, but not less than annually, evaluated to determine if they are to be retained or sent for disposal.

3.5.6 Chemicals Used by Departing Workers

RIs shall ensure that workers moving out of a lab or shop either dispose of hazardous chemicals for which they are responsible as hazardous waste, or transfer unused or partially used hazardous chemicals to others before leaving. Chemicals that are still usable but no longer needed should be recycled through the CHEW, if it is safe to do so. See Documents 12.7, €œShutdown or Transfer of Facilities, Operations or Associated Equipment,€� and 12.8, €œDecontamination and Disposition of Process-Contaminated Facilities and Associated Equipment,€� in the ES&H Manual for requirements relating to chemicals in an activity that is being discontinued and for facilities being demolished or entering inactive status, respectively.

3.6 Labeling and Signage

This section addresses labeling and signage requirements.

3.6.1 Labeling

Proper labeling of hazardous chemicals warns users of hazards that may include environmental aspects and helps ensure that eventual disposal is carried out properly. Workers shall read the label of any chemical they are using for the first time to determine if it is hazardous, what the hazards are, and to identify appropriate controls.

RIs shall ensure that the labeling requirements of Documents 10.2 regarding labeling chemical containers, and requirements of Document 14.2 regarding labeling chemicals in laboratories are met.

3.6.2 Signage

RIs shall ensure that areas where chemicals are used and stored are posted with the appropriate signs, and that Documents 10.2 and 14.2 requirements for signs are met. Signs for specific chemicals or chemical classes are noted in the chemical-specific documents in Part 14 of the ES&H Manual.

For both laboratory and nonlaboratory areas, the RI shall indicate, or arrange to indicate, the hazards present by generic categories (e.g., corrosive, flammable, oxidizer, reducing agent, explosive, highly toxic, and reactive) on the Hazard Notice Door Signs, as specified in Document 10.2.

3.7 Chemical Handling

This section discusses the requirements for handling solid and liquid chemicals, gases, peroxides, and peroxidizable materials.

3.7.1 Precautions for Handling Hazardous Solid and Liquid Chemicals

Workers shall:

• Keep the work area as clean and orderly as the operation will allow.
  
  
• Use exhaust ventilation (e.g., laboratory hoods, flexible duct exhausts, lateral exhaust hoods) to minimize personnel exposures to air contaminants when performing operations that can generate air contaminants (e.g., aerosols and gases/vapors), unless the ES&H Team has evaluated the work and approved performing the work without these controls. See Documents 12.2, 12.3, 12.4, and 12.5 for planning and using exhaust ventilation.
  
  
• Use protective equipment such as safety shields and enclosures, and lower the sashes of laboratory hoods so the face is protected from spatter and splinters. Enclosures also maximize protection provided by exhaust ventilation.
  
  
• Do not eat, drink, smoke, or apply cosmetics, or store these items in an area where hazardous chemicals are handled.
  
  
• Wash hands immediately after handling all chemicals, regardless of whether gloves have been worn.
  
  
• Use mechanical aids for all pipetting procedures (never mouth pipette).
  
  
• Evaluate hazards and environmental aspects and identify proper containers and controls before transferring or dispensing chemicals from manufacturer-supplied chemical containers.
  
  
• Provide secondary containment for retaining spills as appropriate.
  
  
• Limit the volume of volatile or flammable chemicals, preferably to the amount required for daily operations.
  
  
• Follow the requirements in Document 18.1, €œPressure,€� in the ES&H Manual if the operating system is used under pressure or if it can generate pressure.
  
  
• Keep hazardous chemicals out of offices.
  
  
• Use the required PPE as specified in Document 11.1.

To the extent feasible, workers should observe the following guidelines:

• Isolate hazardous operations by performing them in separate rooms and limit the number of workers involved.
  
  
• Assure that safe and convenient lavatory facilities are available.
  
  
• Do not use solvents for personal cleanup.

Facility management shall ensure that break areas are not located where hazardous chemicals are handled or stored.

Newly synthesized chemicals, of which the toxicity, chemical, and physical properties have not been fully characterized or studied, shall be considered hazardous by all workers. Therefore, use only a small quantity of these chemicals to minimize both the effects of unexpected reactions and the potential for toxicity resulting from exposure.

The Hazards Control Department is responsible for conducting the workplace chemical hazard monitoring. This monitoring measures or otherwise evaluates the extent of an employee€™s exposure to hazardous chemicals and assesses compliance with regulations and documenting the monitoring results. This activity is described in more detail in Document 10.2.

3.7.2 Handling Chemically-Hazardous Gases

Workers who handle gases shall be familiar with their properties and health effects, and exercise care in handling them. Gases may be corrosive, flammable, toxic, radioactive (e.g., tritium), or explosively reactive when they come into contact with other chemicals (including air, water, or nonhazardous chemicals).

RIs shall be familiar with Document 18.1, Document 18.5, €œCryogens€�; and 14.3, €œToxic, Corrosive, or Reactive Gases€� in the ES&H Manual. For detailed information on specific gases, especially those that are toxic, see:

• Matheson Gas Data Book.
  
  
• Fire Protection Guide on Hazardous Materials (National Fire Protection Association).
  
  
• The area ES&H Team.

3.7.3 Peroxidizable Chemicals

Workers shall implement the requirements specified in LLNL€™s Standard for Storing and Using Peroxidizable Organic Chemicals (UCRL-AR-133218, Rev. 1), when working with peroxides or peroxidizable chemicals. This standard contains requirements for special labeling and periodic testing of contents and can be found at the following intranet address:

http://www.llnl.gov/tid/lof/documents/pdf/235232.pdf

Peroxidizable chemicals form unstable peroxides when they are in the presence of oxygen, stored for long periods of time, or exposed to light. Peroxides may also be formed even if preservatives or inhibitors are added to slow down the peroxidization process. These chemicals may explode when disturbed, when the caps are removed from their containers, or when they are used. Thus, these chemicals shall be protected from exposure to light, heat, and air. The chemicals indicated as High Hazard in Table 2 shall be stored under inert gas, while the remaining chemicals listed in Table 2 are stored in sealed containers.

In addition, workers shall store peroxidizable chemicals in accordance with the time limitations specified in Table 2. Old containers of peroxide-forming chemicals improperly stored are most likely to be dangerous, especially if discoloration, crystallization, or layering is observed. If you believe that dangerous levels of peroxides may be present in a container (e.g., observing visible signs of deterioration as listed in Section 3.5.3), immediately contact the Fire Department [dial 911 or, if using a cellular phone or dialing from offsite, 1 (925) 447-6880]. The Fire Department manages the response until it is determined that the container does not pose an imminent hazard.

Peroxidizable chemicals are the best understood of the chemicals with age-related hazards. However, age has played a role in incidents involving other types of chemicals. Chemical/Biological Safety (CBS) shall set hazardous chemical age-related limits based on known safety considerations using available information, including consultation with knowledgeable people (e.g., chemists performing research using such chemicals). Most chemicals will not be affected by safety-related age limits.