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Requirements:
Procedures and Specific Requirements

Chemical Hygiene Program

Written Chemical Hygiene Plan

The Chemical Hygiene Plan [pdf] provides guidelines and specific requirements for the development of laboratory-specific chemical hygiene plans. Prior to working in any laboratory with a CHP, personnel must acknowledge in writing that they have read and are familiar with the laboratory chemical hygiene plan and will comply with the requirements of the plan.

Obtaining Conditional Exemptions/Determination of Facilities Covered by the CHP

Determination of facilities covered by the CHP is the responsibility of the industrial hygiene program manager.

Hazardous Materials Management

Chemical Use Planning

Prior to using a new chemical, personnel and supervisors will plan for that use. (See Hazardous Materials: Chemical Use Planning Guidelines [pdf].)

Chemical Acquisition

All chemical purchases at SLAC are processed through a centralized chemical management and information system called Haas tcmIS. Only employees authorized by their supervisors may place orders for chemicals through tcmIS. Access to the system for ordering privileges must be coordinated through the hazardous materials program manager. SLAC personnel with current ordering privileges are listed on the chemical management services (CMS) web site. It should be noted that approval of an order through the approval hierarchy is acknowledgement of financial responsibility and is in effect an approval of the invoice. In addition, contact information for ES&H and Haas tcmIS on-site representatives who can assist with this procedure are also included at this web site. Once access is granted and an approval hierarchy is set up for that user, he/she will be trained by the hazardous materials program manager and/or Haas tcmIS on-site customer service representative on how to order and track chemical purchases.

The process description and flow diagram for chemical purchasing Hazardous Materials: Purchasing Flow Chart [pdf].

No other means of acquiring chemicals for on-site use is permitted without prior management approval and program review. Possible ramifications for purchases made outside of this policy include the following sanctions:

• Petty cash purchases: no reimbursement will be issued
• P-card purchases: first violation, verbal warning and written warning; second violation, p-card revoked
• All purchases: note of infraction(s) placed in annual performance review

Lead Acquisition

Raw metals are not covered by the current implementation of the CMS system. The specific requirements on elemental lead and lead shielding are covered in detail in Chapter 20, "Lead Safety", and any subsequent clarifications issued by either the hazardous materials or the industrial hygiene program manager.

Ethanol Acquisition

The purchase and use of ethanol is regulated by the United States Department of the Treasury, Bureau of Alcohol, Tobacco, and Firearms. There is a federal excise tax on the use of ethanol; however, tax-free alcohol may be used for scientific, medicinal, and mechanical purposes. SLAC receives its research-use ethanol through an agreement with Stanford University stores as the university has a permit under the tax-free exemption. Users of ethanol must coordinate their purchase through the hazardous materials program manager. (See Hazardous Materials: Ethanol Purchasing Procedure [pdf].)

Hazardous Waste Minimization and Pollution Prevention

Waste minimization is defined as measures that reduce the volume and toxicity of hazardous waste disposed in landfills. Pollution prevention is a broader term that includes waste minimization. Pollution prevention is defined as measures that reduce the generation of non-hazardous and hazardous waste, and prevents deterioration of the earth's atmosphere, water, land, and biota caused by pollution. Pollution prevention includes resource conservation and spill prevention. Waste minimization and pollution prevention program requirements are provided in Chapter 22, "Waste Minimization and Pollution Prevention". The waste minimization and pollution prevention program is inextricably bound to the hazardous materials program, as the objectives are the same: to reduce waste and toxicity whenever possible.

Inspection and Delivery

All chemicals are required to be transported to SLAC by one of two means: by Haas CMS vendor subcontractors or by delivery personnel working for Stanford University Stores. No exceptions are allowed without prior management approval and program review.

Chemical containers shipped to SLAC through the Haas hub will be inspected and bar-coded at the hub prior to their arrival on site. Chemicals directly shipped to SLAC from the manufacturing location and materials shipped from Stanford University Stores will be inspected upon delivery.

Chemical Storage

The amount of chemicals stored on site should be kept to a minimum. When storage is necessary the following requirements apply.

Storage Assets

As described in 5.1.4.3 (General Requirements, Hazardous Materials Management, Chemical Storage Assets), there are eight classes of storage assets in use at SLAC, subject to the stated requirements. Requirements for using storage assets safely are in Hazardous Materials: Chemical Storage Asset Requirements [pdf].

Incompatibility

Many chemicals are incompatible with one another and must be kept separate. This can be accomplished by distance or by secondary containment, depending on the type of incompatibility, the severity of any possible reactions, and the quantities of the respective chemicals.

Incompatible materials must be separated when the stored materials are in containers having a capacity of more than five pounds (2.3 kg) or 0.5 gallon (1.9 L). Separation can be accomplished by one of the following techniques:

• Segregating incompatible materials storage by a distance of not less than 20 feet (6.1 m)
• Isolating incompatible materials storage by a noncombustible partition extending not less than 18 inches (0.46 M) above and to the sides of the stored material
• Storing liquid and solid materials in hazardous materials storage cabinets
• Storing compressed gases in approved gas cabinets or exhausted enclosures

Materials that are incompatible may not be stored within the same cabinet or exhausted enclosure.

Do not store chemicals alphabetically as a general group. Chemicals may be separated into compatible groups and stored alphabetically within those compatible groups. Observe all precautions regarding the storage of incompatible chemicals and refer to the MSDS and any applicable SLAC chemical handling and safe use guidelines. (See Forms & Exhibits) A wall chart listing common chemical incompatibilities is available through SLAC Stores.

The National Oceanic and Atmospheric Administration (NOAA) has made available a reference tool that allows one to identify the reactivity of substances or mixtures of substances. This chemical reactivity tool is a database of reactivity information for more than 6,000 common hazardous chemicals where one can determine what dangers could arise from accidentally mixing incompatible chemicals. (See “The Chemical Reactivity Worksheet” (Home>Software & Data Sets>Planning for Environmental Emergencies>The Chemical Reactivity Worksheet)

Secondary Containment

Secondary containment is used because equipment or containers could break, leak, or spill their contents. The type of secondary containment used must be chemically compatible with the hazardous material being stored. Secondary containment is required if any of the following conditions are met:

1. Any hazardous material is stored in single containers in excess of 55 gallons of liquid, 550 lbs for solids, or when the aggregate capacity of multiple vessels exceeds 1,000 gallons (10,000 lbs for solids)
2. Any hazardous material is stored that if it escapes from its primary container may threaten personnel or the environment (for example, contaminates soil or water)
3. Any hazardous material is stored that if it escapes from its primary container could come in contact with another material with which it could produce an incompatible chemical reaction (for example, emitting toxic gas, igniting, or exploding)

Secondary containment must be designed so that it contains 110 percent of the volume of the primary container. If any storage or use area will hold multiple containers, the secondary containment must hold either 10 percent of the aggregate volume or 150 percent of the largest container, whichever is greater. If the hazardous material is stored in an interior hazardous materials storage room, the secondary containment must also be able to contain 20 minutes of sprinkler flow, at the design flow rate for that area, plus the volume of the chemical container. If the hazardous material is stored in an exterior storage area and open to rainfall, it must be designed to contain the volume of the chemical container plus the volume of a 24-hour rainfall as determined by a 25-year storm and provisions shall be made to drain accumulations of the rainwater.

Incompatible materials will not be stored within the same secondary containment. See Hazardous Materials: Secondary Containment Requirements [pdf] and Chapter 16, "Spills", for more information.

Time- or Shock-sensitive Chemicals

Because many chemicals cannot be stored indefinitely, the user should establish shelf-life guidelines. Materials whose hazardous properties may change upon storage should be dated when first opened. Chemicals that form peroxides or shock-sensitive characteristics should be marked in accordance with the criteria set forth for unstable, time-sensitive, and pyrophoric materials.

Other Chemical Storage Considerations

Other best management practices to follow in the storage of chemicals include the following:

• Provide a designated storage place for each chemical and return the chemical to that location after each use.
• Store chemicals at or below eye level; keep lids and caps on securely when returning to storage.
• Avoid storing chemicals on bench tops, except for chemicals currently being used.
• Do not store chemicals in laboratory hoods except for those currently in use.
• Do not expose stored chemicals to direct heat or sunlight unless in approved cabinets.

Chemical Storage Inspections

Each chemical storage asset and area will be assigned a custodian, and each custodian is responsible for ensuring that periodic inspections of the asset and area are performed. Informal inspections are expected to occur daily. This simply involves observation of the asset and the chemicals contained therein to ensure that there are no leaks or spills.

A formal documented inspection of hazardous materials storage assets and areas will occur monthly. (See Hazardous Materials: Storage Inspection Procedure and Form.) The custodian is responsible for maintaining these inspection reports for at least one year.

Refer to Chapter 17, "Hazardous Waste", for information about hazardous waste inspections and the hazardous waste inspection checklist.

Labeling and Signs

Labels are used to provide critical health and safety information to personnel handling and using hazardous chemicals and products containing hazardous chemicals. Labels or other forms of warning such as signs must be legible, in English, and prominently displayed on the container. Other languages may be added to convey information as long as the information is presented in English as well. When the marking or labeling is impractical due to the size of the container, other solutions, such as a tray in which the container is located, or a tag attached by a wire loop, may be used. Refer to Chapter 17, "Hazardous Waste", for an example of approved hazardous materials labels.

Hazardous Materials Inventory

The Haas tcmIS is used to track chemicals on site and to maintain inventories. Individuals can request the information from the hazardous materials program manager. This inventory will be reconciled annually by ES&H staff, with assistance as necessary from the chemical asset custodians, and will be submitted by the hazardous materials program manager to the SLAC CUPA (San Mateo County) to satisfy hazardous material business plan reporting obligations.

Chemical Use Reporting

SLAC has reporting requirements for numerous external environment, safety, and health (ES&H) programs associated with chemical use, as well as internal reporting programs required by the DOE. Some of the more important programs that require such information include the SLAC annual emissions report under Title V of the Clean Air Act, its hazardous materials business plan, and its toxic release inventory (TRI) submittals. The hazardous materials program manager has the responsibility to establish the necessary Haas tcmIS reporting templates in support of ES&H program managers who prepare and submit chemical usage reports using Haas tcmIS reporting capabilities. (Further information is provided in Hazardous Materials: Purchasing Flow Chart [pdf].)

Sharps Disposal

Sharp objects such as needles, syringes, and razors require storage and handling to prevent accidents to workers. For proper disposal of sharp objects, please see Chapter 46, "Blood-borne Pathogens". Sharp items that are not contaminated with bodily fluids, but may have been contaminated by a hazardous substance should be treated as hazardous waste, and special consideration should be given to minimize the risk of cuts. Some sharp objects may need additional labeling and handling based on their hazardous and radioactive constituents. Consult the Waste Management Group or the Radiation Protection Department for further guidance and requirements (chapters 17, "Hazardous Waste", and 9, "Radiological Safety").

Industrial Hygiene

Industrial hygiene (IH) monitoring is the measurement of chemical, physical, and biological hazards in the workplace. Chemical hazards exist when there is a risk of direct skin contact, inhalation, ingestion, or absorption of hazardous chemicals in the form of liquids, solids, vapors, gases, dusts, fumes, or mists. The degree of risk associated with handling a specific chemical depends on the toxicity of the chemical and the magnitude and duration of exposure. Chapter 5, "Industrial Hygiene", provides all of the applicable information regarding this program and its implementation at SLAC.

Accidental Exposures

Inhalation Exposures

Many chemicals can become airborne as gases, mists, vapors, or dusts. Exposure through the respiratory system can be very dangerous because absorption into the blood stream through the lungs occurs quickly. In addition, many materials can damage the nose, throat, and lungs directly. Persons over-exposed to chemicals should immediately be relocated to fresh air and be provided with medical attention. This may include the administration of oxygen as well as other medical treatment. Emergency response should be notified as soon as possible by dialing 911.

Eye Contact

Many chemicals will damage the eyes if contact occurs. If a chemical contacts the eyes, immediately flush the eyes with copious amounts of water, preferably at the nearest eyewash station. A minimum of 15 minutes rinse time is required. Emergency response should be notified as soon as possible by dialing 911. Do not stop flushing the eyes until emergency personnel arrive on the scene and inform you to stop flushing.

Skin Contact

If a chemical comes into contact with the skin, immediately rinse the affected area with large amounts of running water. This may be done in a sink if the hands are the only portion of the body contacted or under a safety shower if the exposure area is more extensive. Emergency response should be notified as soon as possible by dialing 911 if the chemical is a corrosive or could have been absorbed through the skin. Remove contaminated clothing while under the shower. Remain under the shower until emergency personnel inform you to stop, or for a minimum of 15 minutes.

Eyewash and Safety Showers

Eyewash stations and safety showers help protect SLAC personnel after an accidental eye or skin exposure to corrosive or flammable materials. Eyewash stations are required in areas where personnel can come into contact with corrosive liquids or gases. SLAC relies on the departments responsible for areas with eye or skin hazards to inspect and ensure the reliability of eyewash stations and safety showers.

Installation, removal, or change of location for any chemical emergency equipment (such as eye washes and safety showers) must have prior approval by the directorate ES&H coordinator or hazardous materials or industrial hygiene program manager.

Where there is a potential for personnel to be exposed to injurious corrosive materials, the line manager will ensure appropriate eyewash and shower equipment is available within the work area. Emergency eyewashes, showers, and drench hoses, however, are not substitutes for proper primary eye and face protection such as safety glasses, chemical splash goggles, face shields, and protective clothing.

Supervisors (or designees) that are responsible for areas where eyewash stations or safety showers exist must know the equipment location, inspect the equipment, provide for equipment maintenance, and notify appropriate personnel to repair or replace the equipment if it is missing, defective, or inoperative.

Below are some of the recommendations and requirements from the ANSI standard (Z358.1-1998) for eyewash station and safety shower equipment. For more details about inspections and maintenance that are not covered in this summary, please refer to the ANSI standards directly (a copy is available in ES&H). (also see the SLAC Library for availability of a hard copy.) The standards summary is provided here as basic reference for supervisors or their designees responsible for equipment maintenance.

• Plumbed eyewashes will be flushed weekly to minimize the accumulation of sediment and other obstructions. Safety showers will be flushed monthly. Flush until the fluid runs clear.
• Each eyewash station and safety shower will be inspected weekly. Log inspections by marking the inspector's name and inspection date on a tag attached to the equipment. Inspection tags are available from SLAC Stores. (See Hazardous Materials: Eyewash/Shower Inspection Form.)

The eyewash station or safety shower must comply with the following requirements:

1. Located as close as possible to the chemical use location, preferably within a travel time of ten seconds from areas where eye or skin hazards are present (consult CGS if there are questions about locations and hazards)
2. Clearly marked
3. Protected from freezing conditions
4. Provided with a path of travel free of obstructions, including closed doors
5. Installed and maintained with no sharp projections in the operating area
6. On the same floor or level as the hazard
7. Equipped with a valve that can be activated in one second or less, (equipped with a crash bar, lever, or pedal, as opposed to a screw-type valve)
8. Equipped with a hands-free feature that allows for water flow while one's hands are opening eyelids or removing clothing
9. Capable of flushing both eyes simultaneously (eyewashes only)
10. Protected with nozzle caps or bowl covers (eyewashes only)
11. Capable of delivering no less than 0.4 gallons (1.5 liters) of water per minute for fifteen minutes for eyewashes 20 gallons (75.7 liters) of water per minute for 15 minutes for safety showers

Note Hand-held drench hoses may be installed to supplement an eyewashes or showers, but may not replace them.

Self-contained eyewash units may be used in areas where it is not feasible to install plumbed units. Where the possibility of freezing conditions exists, units will be protected from freezing, or freeze-protected equipment will be installed.

Tepid water will be provided at all newly installed eyewashes and safety showers, and should be provided at existing installations whenever possible. The term tepid is defined by ANSI as moderately warm or lukewarm, but ANSI does not specifically define a temperature range for tepid water. The SLAC ES&H Division agrees with the general industry consensus that tepid water should range from 60 to 92°F (15 to 33°C). (See Hazardous Materials: Eyewash/Shower Inspection Procedure [pdf] and Hazardous Materials: Eyewash/Shower Inspection Form.)

Personal Protective Equipment

The use of personal protective equipment (PPE) is required in some areas at SLAC for protection of workers from various chemical hazards. PPE is not a substitute for adequate engineering or administrative controls and should be used only if no other measures are adequate or feasible. A description of PPE for chemical hazards is provided in Hazardous Materials: Personal Protective Equipment Requirements [pdf]. Refer to Chapter 19, "Personal Protective Equipment", for complete requirements related to PPE, including PPE: Reimbursement Procedure [pdf] and PPE: Prescription Safety Glasses Approval Form.

Fire Prevention

The following requirements are specific to fire hazards of hazardous materials. See Chapter 12, "Fire and Life Safety", for complete information about fire prevention, protection, and suppression.

• Take measures to prevent ignition of flammables. Smoking, welding, cutting, grinding, and using open flames or ordinary electric equipment in the vicinity of flammable materials is prohibited. Consult the fire marshal for specific distance requirements. NO SMOKING signs must be posted on or near storage cabinets for flammables and in areas where flammables are stored, handled, or used. NO SMOKING signs and FLAMMABLE signs and labels are available from SLAC Stores.
• Anticipate the type of fire extinguisher required should an experiment or other use of chemicals result in a fire. The fire marshal may be contacted for information regarding type, spacing, and location of fire extinguishers.
• Equipment and containers dispensing flammable or combustible liquids must be properly bonded and grounded to prevent the accumulation of static and a potential ignition source.
• Electrical wiring and equipment in close proximity to flammable and combustible liquids, flammable gases, and flammable solids, must be installed and maintained in accordance with the National Electrical Code and articles 79 and 80 of the Uniform Fire Code. (Hard copies of NFPA 70-2005 and ICBO UFC-1997 are available from the SLAC Library.) Such operations must be classified appropriately and the appropriate class of electrical equipment must be used (the fire marshal should be consulted to assist in this classification).
• An open flame should only be used when necessary and extinguished when it is no longer needed. For additional information see Fire and Life Safety: Fire Prevention Hot Work Guidelines [pdf].
• Personnel working in a chemical area should become familiar with the following information:
• Location and use of the nearest fire extinguishers
• Location and use of the nearest eyewash station and safety shower
• Location and use of any chemical-specific antidotes
• Location and route to the nearest emergency exit
• Location and use of the nearest fire pull box and telephone for emergency notification
• Location and proper method for de-energizing and/or isolation of hazardous equipment or processes

Refer to Fire and Life Safety: Limiting Fire Hazards Guidelines [pdf] for further information.