GN470094, Handling Chemicals at SNL/CA
Sponsor: Michael W. Hazen, 4000
Revision Date: October 31, 2008
Replaces Document Dated: October 16, 2007

This document is no longer a CPR. This document implements the requirements of Corporate procedure ESH100.2.IH.25, Control Chemical Hazards at SNL/CA.

IMPORTANT NOTICE: A printed copy of this document may not be the document currently in effect. The official version is the online version located on the Sandia Restricted Network (SRN).


GN470094 – HANDLING CHEMICALS AT SNL/CA


Subject Matter Expert: Al Buerer
GN470094, Issue E
Revision Date: October 31, 2008; Replaces Document Dated: October 16, 2007


Change History

Note: Chemicals can present a variety of hazards. A good source of information on chemical hazards is the Sandia Chemical Information System (CIS). The CIS contains a database of Material Safety Data Sheets. In addition, the CIS contains lists of chemicals according to various hazard categories and can search chemical inventories according to the categories. The following are examples of some of these lists of chemicals. The user can consult the CIS for a complete list of such documents as needed.

These lists must be used with caution, because in general, exposure quantities or paths that produce the effects indicated are not included in the lists. These lists are intended to serve only as a preliminary source of information for evaluating laboratory risks. Additional factors, such as quantity of chemicals used, frequency and duration of use, physical and chemical properties, and exposure control measures need to be considered to determine the overall risk potential of a chemical.


1.0 PURPOSE, SCOPE, AND OWNERSHIP

1.1 Purpose

This supplement governs the acquisition, storage, use, and disposal of hazardous chemicals for both the OSHA Hazard Communication Standard and the Laboratory Standard at SNL/CA. The intention of this document is to ensure that routine chemical operations at SNL/CA are conducted in such a way as to minimize the risk to Members of the Workforce, threat to the environment, and the generation of hazardous waste. This document supplements ESH100.2.IH.4, Evaluate and Control Chemical Hazards.

This document is not intended to provide all-inclusive requirements or guidance for chemical operations, but should be used in concert with other Sandia Requirements documents such as the ES&H Corporate Procedures.

This document governs the use of hazardous chemicals. This document does not govern the use of the following materials, equipment, or systems:

It is the joint responsibility of department managers and owners of chemical work areas to determine whether any specific operation requires an activity-specific Technical Work Document (TWD). Call the ES&H Hotline at 294-3724 or review ESH100.2.GEN.3, Develop and Use Technical Work Documents if assistance is needed.

1.2 Applicability

For purposes of this document, Members of the Workforce are:

This section applies to all Members of the Workforce who handle chemicals at SNL/CA.

1.3 Ownership

The Health and Safety Department (8517) is responsible for this document. Send suggested changes to Al Buerer, MS 9221.


2.0 RESPONSIBILITIES

2.1 General

The safe handling of hazardous chemicals is an individual responsibility. Management responsibility lies with department managers and with delegated individuals for a particular operation. All personnel must understand that chemical safety is an integral part of the job and not an optional function. There is no activity that is so urgent that it is necessary to compromise safety or to endanger the environment.

During any operation, anyone may question the safety of any aspect of an activity and may at any time request and be granted the immediate cessation of the activity. Such requests should be made to the department manager or person conducting the operation at that time. The department manager has the authority to make an initial evaluation and decision to stop or to continue the operation. However, the individual questioning the safety of the operation should contact their center director if the question is not resolved satisfactorily. If the operation is immediately dangerous to life or health, the individual questioning the safety of the operation is authorized to immediately terminate the operation in a manner that eliminates or reduces the hazard and does not introduce new hazards that are immediately dangerous to life or health.

Support regarding safe handling of chemicals as related to the OSHA Hazard Communication Standard and the Laboratory Standard at SNL/CA is available from the Industrial Hygienists in the Health and Safety Department, Organization 8517. The individual Industrial Hygienists provide this support based on specific building assignments. Contact the ES&H Coordinator for your Department or call the ES&H Hotline at 294-3724 as needed to obtain Industrial Hygiene support for assessing chemical hazards and controls.

2.2 Center Directors

Center directors have the ultimate responsibility and authority to ensure that all experimental and support activities within a center are conducted in compliance with ES&H Corporate procedures, with applicable federal and state laws and regulations, with this supplement, and with the specific ES&H technical work documents (TWDs) written for each experiment or hazardous operation.

Center directors have other specific responsibilities as indicated in ES&H Corporate procedures, and ESH100.2.IH.4, Evaluate and Control Chemical Hazards.

2.3 Department Managers

Department managers shall perform these tasks:

2.4 Individual Laboratory Owners and Workers

Each individual laboratory owner or worker (including non-permanent employees and contractors) is responsible for the following tasks:

Laboratory owners and personnel who perform work in a laboratory that is designated as an OSHA Laboratory Standard location have other specific responsibilities as indicated in ESH100.2.IH.4, Evaluate and Control Chemical Hazards.

2.5 Visitors

2.5.1 Casual Visitors

All casual visitors who enter chemical work areas shall be familiar with the types of chemical hazards and any special precautions for the area.

2.5.2 Non-Casual Visitors

Non-casual visitors must meet site-specific training requirements for the Hazard Communication Standard or Laboratory Standard.

2.6 Chemical Hygiene Officer

The Sandia Chemical Hygiene Officer is the SNL/NM Subject Matter Expert for ESH100.2.IH.4, Evaluate and Control Chemical Hazards. This position currently resides in the Industrial Hygiene Compliance Services and Radiation Protection Laboratories Department (4121).


3.0 DEFINITIONS

Action level - The chemical specific exposure level (concentration of material in air) which is generally considered to be one half the TLV or PEL. When the action level is reached, measures are taken to reduce exposures. Such measures may include the use of engineering or administrative controls. Requirements for medical surveillance may also apply.

Acutely toxic - A substance that has been found to have adverse effects resulting from a single dose or a short-duration exposure.

Carcinogen/select carcinogen - Any substance which meets one of the following criteria:

Casual visitors - A casual visitor is one who comes to chemical work areas for a short time duration. The casual visitor may be present for a briefing or a tour, to observe a specific experiment, to consult with a staff member, to collect chemical waste, to perform maintenance or janitorial duties, etc. Casual visitors do not actively engage in experiments or other chemical operations.

Chemical work area - A workplace where chemicals are used.

Chlorofluorocarbons (CFCs) - These are perhalogenated compounds (also called Freons) that are non-toxic and chemically quite stable.

Chronically toxic - A substance that has been found to have adverse effects which become evident after repeated doses, long-duration exposure, or a long latency period.

Combustible liquid - Any liquid having a flash point at or above 100°F (37.8°C), but below 200°F (93.3°C). Also, any mixture having components with flash points of 200°F (93.3°C) or higher, the total volumes of which make up 99% or more of the total volume of the mixture.

Compressed gas - A gas that falls into one of the following categories:

Corrosive - A chemical that causes visible destruction of, or irreversible alterations in, living tissue by chemical action at the site of contact. This term does not refer to action on inanimate surfaces.

Designated area - (Applies to OSHA Laboratory Standard locations.) An area that may be used for work with particularly hazardous substances. A designated area may be the entire laboratory or a device such as a laboratory hood.

Environmental hazard - Materials that are of environmental concern. Examples are volatile organic compounds (VOCs), chlorofluorocarbons (CFCs), and greenhouse gases.

Explosive - A chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature.

Flammable - A chemical that falls into one of the following categories:

Flammable aerosol - An aerosol that, when tested by the method described in 16 CFR 1500.45, yields a flame projection exceeding 18 inches at full valve opening, or a flashback (a flame extending back to the valve) at any degree of valve opening.

Flammable gas - A gas that, at ambient temperature and pressure, forms a flammable mixture with air at a concentration of 13% by volume or less, or a gas that, at ambient temperature and pressure, forms a range of flammable mixtures with air wider than 12% by volume, regardless of the lower limit.

Flammable liquid - A liquid that can be readily ignited at room temperature. Defined by the National Fire Protection Association (NFPA) and the Department of Transportation (DOT) as a liquid with a flash point below 100°F (38°C).

Flammable solid - A solid, other than a blasting agent or explosive, that is liable to cause fire through friction, absorption of moisture, spontaneous chemical change, or retained heat from manufacturing or processing, or which can be ignited readily; and when ignited burns so vigorously and persistently as to create a serious hazard.

Flash point - The minimum temperature at which a liquid gives off sufficient vapor to first form an ignitable mixture with the air near the surface of the liquid or within a test vessel.

Greenhouse gases - Gases that persist in the atmosphere and are implicated in long-term warming of the earth.

Hazardous chemical - A chemical for which there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees. The term "health hazard" includes chemicals which are:

Hazardous waste - Hazardous waste at SNL/CA is any waste that is chemical in nature and either meets the definition of ignitability, corrosivity, reactivity, or toxicity; or is specifically listed in Title 22 of the California Code of Regulations (see ESH100.2.ENV.15, Manage Hazardous Waste at SNL/CA). Most chemicals are required to be managed as hazardous waste when discarded at SNL/CA.

Health hazard - See the definition for "Hazardous Chemical."

IDLH - Immediately dangerous to life and health. The maximum concentration of an airborne chemical from which an individual could escape within 30 minutes without a respirator and without experiencing any escape-impairing or irreversible health effects.

Irritant - A chemical, which is not corrosive, but which causes a reversible inflammatory effect on living tissue by chemical action at the site of contact as a function of concentration or duration of exposure. A substance that produces an irritating effect when in contact with skin, eyes, nose, or respiratory systems.

Laboratory - (Applies to OSHA Laboratory Standard locations.) A facility where the "laboratory use of hazardous chemicals" occurs. It is a workplace where relatively small quantities of hazardous chemicals are used on a non-production basis.

Laboratory scale - Work with substances in which the containers used for reactions, transfers, and other handling of substances are designed to be easily and safely manipulated by one person. "Laboratory scale" excludes those workplaces whose function is to produce commercial quantities of materials.

Laboratory use of hazardous chemicals - (Applies to OSHA Laboratory Standard locations.) Handling or use of such chemicals in which all of the following criteria are met:

LC50 - Lethal concentration 50. Lethal concentration in air that will kill 50% of an exposed animal population within a specified time.

LD50 - Lethal dose 50. The dose of a substance that causes the death of 50% of an exposed animal population within a specified time from a single-dose exposure to the substance by any route other than inhalation.

MSDS - Material safety data sheet. The form used to inform an employee about the hazards of the materials he/she works with so that he/she knows how the material can be safely handled, used, and stored. OSHA has established guidelines for the descriptive information that should be provided on an MSDS.

Must - Used to designate mandatory actions that are required by center policy and procedures.

Non-casual visitor - Anyone who is not normally assigned to an area, but performs hands-on chemical work.

Organic peroxide - An organic compound that contains the bivalent -O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms has been replaced by an organic radical. As a class, these compounds may be low-power explosives, and are hazardous because of their extreme sensitivity to shock, sparks, or other forms of accidental ignition. All organic peroxides are highly flammable.

OSHA - Occupational Safety and Health Administration. The regulatory and enforcement agency for safety and health in most U.S. industrial sectors.

Oxidizer - A chemical other than a blasting agent or explosive that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases.

Particularly Hazardous Substance - (Applies to OSHA Laboratory Standard locations.) Select carcinogens, reproductive toxins, and substances which have a high degree of acute toxicity.

PEL - Permissible exposure limit. A PEL is the OSHA equivalent to the TLV. See the definitions for "TLV." A PEL is usually expressed as an 8-hour time-weighted average. Ceiling limits may be specified for some chemicals. This concentration, if specified, cannot be exceeded for any part of the work shift. DOE orders mandate adherence to ACGIH TLVs and OSHA PELs, whichever limit is lower.

Physical hazard - A chemical for which there is scientifically valid evidence that it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer, pyrophoric, unstable (reactive), or water reactive.

Pyrophoric - A chemical that will ignite spontaneously in air at a temperature of 130°F (54.4°C) or below.

Reproductive toxins - Chemicals which may present reproductive risk to females or males (mutagens), or developmental risk to the fetus (teratogens). These agents may act on various aspects of the reproductive cycle, from sperm and egg production to latent cancer in offspring.

Secondary chemical container - Any container other than a primary (original) container supplied by a manufacturer.

Sensitive chemicals - Chemicals that can be used as precursors in the synthesis of controlled substances are subject to regulation.

Sensitizer - A chemical that causes a substantial proportion of exposed people or animals to develop an allergic reaction in normal tissue after repeated exposure to the chemical.

Shall - Used to designate mandatory requirements or actions. Indicates actions traceable to laws, regulations, DOE orders, or ES&H Corporate procedures

Should - Used to designate "best practices" and means that the action described is recommended but not required by law.

Target organ effects - Table 1 is a target organ categorization of effects which may occur, including examples of signs and symptoms and chemicals which have been found to cause such effects. Examples are presented to illustrate the range and diversity of effects and hazards found in the workplace, but are not intended to be all-inclusive.

Table 1. Summary of Target Organ Effects

Category Description Signs and Symptoms Examples
Hepatotoxins Chemicals which produce liver damage
  • Jaundice 
  • Liver enlargement
  • Carbon tetrachloride 
  • Nitrosamines
Nephrotoxins Chemicals which produce kidney damage
  • Edema 
  • Proteinuria
  • Halogenated hydrocarbons 
  • Uranium
Neurotoxins Chemicals which produce their primary toxic effects on the nervous system
  • Narcosis 
  • Behavioral changes 
  • Decrease in motor functions
  • Mercury 
  • Carbon disulfide 
  • Lead 
  • Solvents as a general class
Agents which act on the blood or hematopoietic system Chemicals which decrease hemoglobin function, deprive the body tissues of oxygen
  • Cyanosis 
  • Loss of consciousness
  • Carbon monoxide 
  • Cyanides 
  • Benzene
Agents which damage the lung Chemicals which irritate or damage the pulmonary tissue
  • Cough 
  • Tightness in chest 
  • Shortness of breath
  • Sulfur dioxide 
  • Ozone 
  • Bromine 
  • Formaldehyde 
  • Hydrogen sulfide 
  • Nitrogen dioxide
Reproductive toxins Chemicals which affect the reproductive capabilities, including chromosomal damage (mutations) and effects on fetuses (teratogenesis) 
  • Birth defects 
  • Sterility
  • Lead 
  • DBCP 
  • Ethanol
Cutaneous hazards Chemicals which affect the dermal layer of the body
  • Defatting of the skin 
  • Rashes 
  • Irritation
  • Ketones 
  • Chlorinated compounds
Eye hazards Chemicals which affect the eye or visual capacity
  • Conjunctivitis 
  • Corneal damage
  • Organic solvents 
  • Acids

TLV - Threshold limit value. See definition for "TLV-TWA."

TLV--ceiling - Threshold limit value--ceiling. The maximum airborne concentration which should not be exceeded during any part of a work day.

TLV--STEL - Threshold limit value--short-term exposure limit. The 15-minute TWA which should not be exceeded at any time during a work day.

TLV--TWA - Threshold limit value--time-weighted average. Average (usually over an 8-hour period) airborne concentration to which nearly all workers may be repeatedly exposed day after day without adverse effects. This term is usually referred to as "threshold limit value (TLV)." DOE orders mandate adherence to ACGIH TLVs and OSHA PELs, whichever limit is lower.

Toxic - A chemical falling within any of the following categories:

Unstable (reactive) - A chemical which, in the pure state or as produced or transported, will vigorously polymerize, decompose, condense, or become self-reactive under conditions of shock, pressure, or temperature.

Volatile organic compounds (VOCs) - These are gases or liquids and solids with high vapor pressure that could be released to the air. These materials are implicated in the formation of smog and elevation of near-surface ozone levels.

Water-reactive - A chemical that reacts with water to release a gas that is either flammable or presents a health hazard.


4.0 TRAINING

Managers shall ensure that Members of the Workforce complete the required training identified below prior to performing the indicated work activity or fulfilling the indicated role. The most effective method to ensure that hazardous chemicals are handled properly is to ensure that all personnel who handle chemicals are fully informed as to their proper use, storage, and disposal.

All personnel who are engaged in work that involves the handling of hazardous chemicals shall receive basic SNL training appropriate to their work in either a Hazard Communication Standard or a designated OSHA Laboratory Standard location. See the HAZ and LAB series of courses in TEDS Everyone, for a description of applicable training courses.

Work in an office environment which involves the "household use" of chemicals or the use of computers or printer toners for photocopiers and fax machines is governed by the Hazard Communication Standard. These personnel are only required to take the Hazard Communication Briefing included in the ES&H New Employee Orientation.

Additional training may be required depending on the exact nature of the hazards in a particular operation. For example, radiation safety training may be necessary to handle radioactive materials. Department managers shall be consulted for specific training requirements for personnel assigned to chemical work areas.

HR100.2.1, Identify and Complete Sandia Required Training for all Members of the Workforce.


5.0 PROTECTIVE EQUIPMENT

5.1 Hazards

Chemicals present a very broad range of hazards to personnel and to the environment (if they are released). Specific chemicals that represent the full range of chemical hazards are present in many chemical work areas.

5.2 Personal Protective Equipment

Face and eye protection shall be provided and used where chemical splashes present a hazard. The minimum protection is safety glasses with full sideshields for use with small quantities of chemicals that are not highly toxic or corrosive. Chemical splash goggles (with indirect venting) or full face shields with safety glasses shall be used for eye protection when handling materials under the following conditions:

Note: Operations that generate aerosols may also require respiratory protection as described in this section below.

Chemical splash goggles are available from the Health and Safety Department, Industrial Hygiene upon request or they can be purchased through outside suppliers.

Appropriate gloves shall be worn when handling corrosives, irritants, sensitizers, toxic chemicals, particularly hazardous substances, or chemicals with unknown toxicological properties. Gloves should be available in appropriate sizes and materials for the work performed in the area. For guidance in selecting glove materials, consult an industrial hygienist in the Health and Safety Department (8517).

Laboratory coats or other appropriate protective clothing shall be used as appropriate.

A respirator shall be worn if exposure to chemicals will exceed the action level. Use of respirators shall conform to requirements of the Sandia Respiratory Protection Program and ESH100.2.IH.4, Evaluate and Control Chemical Hazards. (applies to designated OSHA Laboratory Standard locations). To become an active user of respiratory equipment, contact the respirator program administrator in the Health and Safety Department (8517). See ESH100.2.IH.3, Control Inhalation Hazards Using Respiratory Protection, for more information

5.3 Containment Devices

Fume hoods or similar containment devices shall be used for experiments that could emit any of the following:

Fume hoods shall be surveyed after installation and annually thereafter. Laboratory owners shall contact an industrial hygienist in the Health and Safety Department (8517) for the survey to be performed. For further information on laboratory ventilation and use of fume hoods, see ESH100.2.IH.15, Control Hazards Using Local Exhaust Ventilation and High Efficiency Particulate Air Filters, and ESH100.2.IH.4, Evaluate and Control Chemical Hazards (applies to designated OSHA Laboratory Standard locations).

Fume hoods shall not be used as storage devices for chemicals or equipment unless required for inhalation safety or allowed by the SNL ES&H Manual. Users shall ensure that:

5.4 Safety Showers and Eyewashes

Every chemical work area shall be evaluated to determine if an eyewash and/or safety shower is required. The requirements for eyewashes and safety showers are listed in ESH100.2.IH.13, Work with Injurious Corrosive Materials and Manage Safety Shower and Eyewash Use. Emergency eyewashes shall be flow tested on a weekly basis. Safety showers shall be tested monthly. Flow testing shall be documented, and documentation maintained for a minimum of 365 days.

5.5 Fire Extinguishers and Telephones

Laboratories shall have access to appropriate fire extinguishers.

Every chemical work area shall be equipped with a telephone or portable communication device such as a radio for emergency use. Telephones shall include stickers with the emergency number and room location.


6.0 PROCUREMENT OF CHEMICALS

6.1 General Procurement Requirements

Before procuring any chemical, laboratory workers shall become familiar with the hazards associated with that material by consulting any of the following:

If a chemical is hazardous (or sensitive), laboratory workers shall:

Personnel must be able to obtain the MSDS and inventory either by accessing the Chemical Information System (CIS), on Sandia's Internal Web at https://webprod.sandia.gov/CIS/svStartup, or by contacting the MSDS Helpline at 294-MSDS, or the ES&H Hotline at 294-3724.

Further information regarding procurement of chemicals is available at the Procurement Card homepage and at the GSS Fisher chemical supplier information page.

6.2 General Procurement Guidance

When procuring chemicals, personnel should avoid ordering excess quantities. For hazardous materials, personnel should not feel constrained to order "catalog" quantities. Many chemical suppliers will supply specific amounts of such items. There will be a price premium, but that is preferable to the price for disposal of excess quantities. Chemical quantities on hand should be limited to the volumes necessary for one supply cycle. Personnel should check the Chemical Information System (CIS) to see if the chemical can be obtained from other onsite locations.

Most chemicals arrive through the Logistics and Procurement Department (8523) and are barcoded and inventoried before delivery to individual chemical work areas; thus chemical inventories are available for review by using the Chemical Information System.

No chemical should be accepted from a supplier if it is incorrectly labeled. The manufacturer's or importer's label must contain the following information:

6.3 Flammable Liquids

See ESH100.2.OTH.1, Manage Fire Protection Requirements for Information

6.4 Sensitive Chemicals

Sensitive chemicals (drugs or drug precursors) shall be procured according to the following:

In addition, personnel ordering such chemicals shall ensure that any other legal restrictions associated with the use of a particular material are obeyed.

6.5 Explosive Chemicals

Procurement of explosive chemicals is not covered in this document. However, certain chemicals are explosive, but may not be identified as such. These materials shall be procured and handled as explosives and their use requires an activity-specific ES&H TWD.

Upon receipt of any explosive chemical, personnel shall ensure that the:


7.0 STORAGE OF CHEMICALS

7.1 General Chemical Storage Requirements

All chemicals shall be stored:

Some chemicals are subject to degradation with time (see Attachment B [Word file/Acrobat file]) and storage of these materials shall be regularly reviewed by the user.

All liquid chemicals in quantities greater than one pint (or 500 ml) shall be placed in a spill tray when they are not in use. Solid chemicals do not require secondary containment provided that they are protected by some other manner against falling and breakage in an earthquake (see “Seismic Considerations,” below). Chemicals requiring secondary containment may be stored in manufactured and approved chemical storage cabinets; additional tubs, trays, etc. are not required if the chemicals are compatible.

Secondary chemical containers shall be labeled with the chemical name and appropriate hazard warning information. For more information, see ESH100.2.IH.4, Evaluate and Control Chemical Hazards.

Seismic Considerations:

Hazardous chemicals or materials stored in glass or other breakable containers shall be protected from breakage during earthquakes. Common methods include storage in cabinets with latching doors, in spill pans at lower locations, or on shelves equipped with earthquake strips, lips, rods, wires or other devices to prevent containers from falling.

7.2 Storage Guidance

A chemical storage shed should:

Stored chemicals should be examined at least annually for signs of deterioration or degradation of container integrity.

7.3 Carcinogens and Select Carcinogens

Carcinogens used in laboratories are a sub-set of chemicals defined by OSHA as “Particularly Hazardous Substances.” See Section 8.4 for a discussion of the use of these materials in laboratories.

OSHA carcinogens which are used in areas other than laboratories may require special controls and monitoring. Contact Industrial Hygiene for an assessment if these materials are used outside of laboratories.

7.4 Flammable Chemicals

Flammable chemicals shall be stored in a flammable storage cabinet. Contact the fire marshal in the Planning and Construction Management Department (8512) for guidance in the placement of flammable storage cabinets. Such cabinets are normally not vented, and vent bungs should be in place (where accumulating vapors pose problems, an industrial hygienist and the fire marshal in Department 8512 should be consulted).

Flammable solids (in amounts greater than two ounces) should be stored in a flammable storage cabinet that has been labeled "Flammable Solids."

7.5 Sensitive Chemicals

Sensitive chemicals shall be stored in a locked storage cabinet, preferably separate from other chemicals. Labels should indicate the specific hazards of the contents and that the contents are "controlled."

7.6 Peroxidizable Chemicals

Note: The provisions within this section contain information regarding the use of peroxidizable chemicals due to the high potential for adverse effects from inappropriate use and/or storage thereof. However, in certain applications, researchers may wish to operate beyond these requirements. An example would be storage of a compound within a sealed ampoule and/or under an inert atmosphere, thus prohibiting contact with air. In these situations, researchers should submit to ES&H for review, a new technical work document (TWD) or revise a current TWD through an Interim Change Notice, or submit an SWP that includes procedures and controls that will be followed to ensure the safety of personnel expected to use peroxidizable chemicals beyond the scope of this document.

Under certain conditions, a number of organic and inorganic chemical compounds used at SNL are capable of reacting with atmospheric oxygen to form peroxide compounds. Many of these peroxides are highly flammable and may explode if exposed to heat, mechanical shock, friction or light. Potential adverse health affects may result if one is exposed to these peroxides should a container rupture. Three lists of common peroxide-forming chemicals grouped by hazard mechanism are found in tables 2, 3, and 4. The SNL chemical inventory can be queried for these listed chemicals using the three CIS queries: Peroxidizable Substances, Peroxidizable Substances (Concentrated), and Autopolymerizable Substances reports). While these are the most commonly encountered peroxide-forming chemicals, these lists are not all inclusive and do not contain all potential peroxide-forming compounds. Consequently, chemical users shall always consult individual MSDSs to ensure they are aware all chemical hazards. Peroxide-forming chemicals have different inherent potentials for forming peroxides, as designated by chemical groups, and therefore some are potentially more hazardous than others. Users can contact Waste Management on the ES&H Hotline at 294-3724 for guidance regarding questions related to peroxide formation.

Storage and Handling of Peroxidizable Chemicals

Chemical owners and users shall be responsible for the safe use and storage of any chemical and especially peroxide-forming chemicals.

Chemical owners and users shall implement one or more of the following controls to minimize the formation of peroxides and to effect proper handling and storage:

Chemical owners and users having containers of peroxide-forming chemicals should dispose of them at or before their expiration date. Disposal must be through Waste Management. Contact Waste Management in a timely manner and complete a Peroxide Chemical Label when it is determined that it is necessary to dispose of the material.

Chemical owners and users shall treat containers of peroxidizable chemicals that meet one or more of the criteria listed below as potentially explosive:

Members of the Workforce shall:

Special Storage: In rare circumstances, some of these materials are stored in special environments, such as under inert atmospheres to limit product degradation. In these cases, it may be permissible to retain these materials beyond normal retention dates, provided a knowledgeable owner can show that potentially dangerous levels of peroxides will not be formed.

Table 2. Chemicals that can form explosive levels of peroxides without concentration.
Container disposal date is 3 months from open date.

Butadienea Chloropreneb
Divinyl acetylene Isopropyl ether
Potassium amide Potassium metal
Sodium amide Tetrafluoroethylenea
Vinylidene chloridea  
a When stored as an inhibited liquid monomer (see Table 3 for additional concerns).
b When stored as a liquid monomer.

Table 3. Chemicals that can form explosive levels of peroxides when concentrated
(such as by evaporation or distillation).

Container disposal date is 12 months from open date.

Acetal Acetaldehyde
Benzyl alcohol 2-Butanol
Chlorofluoroethylenel Cumene (isopropylbenzene)
2-Cyclohexen-1-ol Cyclohexene
Cyclopentene Decahydronaphthalene (decalin)
Diacetylene (butadiyne) Dicyclopentadiene
Diethyl ether Diethylene glycol dimethyl ether (diglyme)
Dioxanes Ethylene glycol ether acetates (cellosolves)
Furan 4-Heptanol
2-Hexanol Methyl acetylene
3-Methyl-1-butanol 4-Methyl-2-pentanol
Methyl-isobutyl ketone 2-Pentanol
4-Pentene-1-ol 1-Phenylethanol
2-Phenylethanol Tetrahydrofuran
Tetrahydronaphthalene Vinyl ethers
Other secondary alcoholsc  
c Where potentially peroxidizable alcohols are used for purposes that DO NOT involve heating, chemical reaction, bulk evaporation or other activities that may stress the peroxidizable material, (e.g., cleaning optics, laser dye mixing), it is not necessary to track and test the containers for peroxidation.

Table 4. Chemicals that may autopolymerize (and thus explode) when relatively
small quantities of peroxides are formed.

Container disposal date is 24 hours without inhibitor from open date.
Container disposal date is 12 months with inhibitor from open date.

Butadiene (stored as a gas)d Chlorobutadiene
Chloroprened Chlorotrifluoroethylen
Styrene Tetrafluoroethylened
Vinylidene chlorided Vinyl acetate
Vinyl acetylene Vinyl chloride
Vinyl pyridine  
d Can form explosive levels of peroxides when stored as liquid without inhibitor. When stored as gas, peroxide accumulation may cause autopolymerization.


8.0 USE OF CHEMICALS

8.1 General Procedures

Personnel shall follow these general procedures for their personal safety and protection of the environment:

In addition, personnel shall follow these general procedures:

8.2 Facilities

Chemical work areas shall be maintained separately from office areas. Wherever possible, such locations should have two exits. For further clarification of this requirement, contact the fire marshal in the Health and Safety Department (8517).

Every chemical work area shall have the appropriate Sandia ISMS sign on every entrance to identify specific hazards of materials contained therein. The names of responsible individuals shall be listed there.

8.3 Emissions Control

All personnel shall conduct operations in a manner that minimizes the emission of all chemicals. Emissions are regulated locally by the Bay Area Air Quality Management District (BAAQMD). If operations that produce or may produce chemical emissions are underway or are being planned, personnel shall contact the Environmental Operations Department (8516) to determine if permits are required, or discuss this information during the Interdisciplinary Team (IDT) review for these operations. If a permit is required, operations shall not proceed until appropriate emissions logging procedures and reporting procedures are in place.

8.4 Particularly Hazardous Substances (Applies to OSHA Laboratory Standard Locations)

Particularly Hazardous Substances (PHSs) shall be handled and stored only in "designated areas." Personnel can determine if chemicals they use are included in these categories by accessing the Chemical Information System (CIS) report and selecting the “PHS” list for their query. A designated area may be an entire laboratory, an area of a laboratory, or a device such as a laboratory hood, or balance. The criteria used to determine the designated area may depend on the physical form (solid, liquid, gas), its physical properties, and the prevalence of use in the laboratory. Access to the designated area should be limited. Anyone working in the designated area must be aware of the substances being handled and the precautions that are necessary.

Laboratories, or areas within laboratories, which are designated areas shall be clearly posted using the ISMS sign or equivalent.

Storage areas shall be clearly labeled with appropriate warning signs that indicate the hazard. Containers that are used for carcinogens shall be so labeled.

8.4.1 Decontamination Procedures

To minimize the potential for contamination, laboratory workers who work with particularly hazardous substances shall:

Laboratory workers must decontaminate affected surfaces within designated areas in response to small spills or when the designated area (including contaminated equipment) is returned to general use. Personnel performing these decontamination activities must wear appropriate personal protective equipment to avoid exposure through skin contact or inhalation and must dispose of all wastes appropriately. The following are guidelines for the decontamination of liquids and powders. Consult the Material Safety Data Sheet for further information.

Liquids:

Powders:

Work with particularly hazardous substances may require personnel to enter a medical surveillance program. See HR100.4.7, Participate in Medical Monitoring/Surveillance for further guidance. Personnel should contact the Health Services Department (8527) or their department manager for details.

8.5 Sensitive Chemicals

Use of sensitive chemicals (drugs or drug precursors) should be held to a minimum. These chemicals may be controlled or illicit drugs or precursors that could be illegally used for the manufacture of such drugs. The primary concern with these chemicals is illegal use rather than chemical safety per se. Their use requires an active inventory procedure. All withdrawals from stock shall be noted and the notation signed by the person making the withdrawal. Department managers shall be responsible for an annual physical verification of inventory and records. Other legal restrictions may also apply to the use of certain sensitive chemicals. Loss or theft of these chemicals can result in serious penalties. Members of the workforce must consult the following before ordering sensitive chemicals:

US Department of Justice Requirements:

http://www.deadiversion.usdoj.gov/21cfr/cfr/index.html

http://www.deadiversion.usdoj.gov/21cfr/cfr/2108cfrt.htm

California State Requirements:

http://caselaw.lp.findlaw.com/cacodes/hsc/11100-11107.1.html

8.6 Gases

The use of compressed gases is governed by MN471000, Pressure Safety Manual. Besides the physical pressure hazard, a number of gases present chemical hazards. Users should check the information in Material Safety Data Sheets, technical specification documents, etc., before using compressed gases.

Personnel should purchase only pressurized containers that can be returned to the vendor. If this is impossible, personnel should contact the Environmental Operations Department (8516).

8.7 Radioactive Materials

Requirements for the use of radioactive liquids, solids, or gases are not included in this document. Such usage requires a separate ES&H TWD. Radioactive materials shall not be brought into a chemical laboratory without permission from the Health and Safety Department (8517). See MN471016, Radiological Protection Procedures Manual, for more information.

Generation of mixed chemical and radioactive waste requires prior approval from the vice president. Contact the Environmental Operations Department (8516) for information on this approval process. Precautions shall be taken in all operations to avoid the generation of mixed waste.

8.8 Personnel Exposures

A variety of chemicals are regulated under 29 CFR 1910.1000. Work with these materials shall conform to OSHA PELs or ACGIH TLVs. Normally, this means using these materials in an operating fume hood or other appropriate hood. If in doubt, personnel should contact an industrial hygienist in the Health and Safety Department (8517) to evaluate exposure in chemical handling operations.

8.9 Synthesized, Formulated, or Modified Materials

Unique chemical compounds or chemical mixtures that have been formulated on site may require an MSDS. Laboratory workers should contact an industrial hygienist the Health and Safety Department (8517) for further information. All personnel preparing such materials shall be familiar with the requirements of the Toxic Substances Control Act (TSCA).

Chemical containers for chemicals synthesized, formulated, or modified by SNL must be barcoded and labeled with the same information that is required for manufacturers' labels (see "6.2 General Procurement Guidelines").

For chemicals synthesized on site, labels should indicate the date prepared and the name of the person responsible for the item. The originator should include as much information about the identity of the item (and its hazards) as possible, including lab references to lab notebooks, where appropriate. The same labeling requirements apply to unknown materials provided for chemical analysis. Personnel should not accept unknown materials/chemicals unless they are properly labeled.

8.10 Medical Surveillance

The Benefits & Health Services Department (8527) must perform medical surveillance tailored to monitor the medical effects of exposure to specific chemicals used in the workplace. Personnel who feel that increased medical monitoring is warranted should talk to their department manager and the Benefits & Health Services Department (8527) about changing their monitoring program.

See ESH100.2.IH.4, Evaluate and Control Chemical Hazards, (applies to OSHA Laboratory Standard locations) for more information.


9.0 EMERGENCY PROCEDURES

9.1 Chemical Spills

For guidance on reporting and cleaning up chemical spills, see ESH100.3.1, Prepare for and Manage Emergencies. Call the ES&H Hotline at 294-3724 for assistance on spill cleanup and reporting.

9.2 Accidents and Medical Emergencies

In the event of an accident or medical emergency, personnel shall take the following actions:
Step Action
1 Dial 911. The appropriate medical, ES&H, and security personnel will be contacted simultaneously.
2 If injuries are the result of hazardous substances, remove the source of the injury (e.g., set chemical container upright, close valve) if this can be accomplished without further risk to personnel.
3 Remove the victim to a safe area if circumstances and injuries allow such action.
4 Notify the department manager and provide information to the center director.

9.3 Explosions and Fires

Personnel shall take the following actions:

Warning: In some buildings, activation of an outside fire alarm does not sound an inside alarm.

Step Action
1 Dial 911. If a phone is not accessible or the building needs to be evacuated, pull a fire alarm box. The appropriate medical, ES&H, and security personnel will be contacted simultaneously.
2 Notify the department manager and provide information to the center director.

9.4 Earthquakes

During an earthquake, laboratory workers must immediately stop all operations, secure any hazardous chemicals in use, and move to a safer area. After the earthquake subsides, laboratory workers should:

Step Action
1 Quickly inspect their immediate area to ensure that hazardous materials are secured and do not pose a threat to personnel.
2 Evacuate the building. Do not use fire alarm pull boxes to evacuate the building during an earthquake, unless there is an actual fire.
3 If there is a chemical hazard that cannot be safely dealt with, immediately call 911. If the phone system is not functioning, inform the building emergency team leader.
4 Before resuming any work, ensure all experimental operations are checked by the principal investigator. ES&H assistance may be requested.


10.0 WASTE STORAGE AND DISPOSAL

See ESH100.2.ENV.15, Manage Hazardous Waste at SNL/CA, for comprehensive guidelines for generators of hazardous waste at SNL/CA.

Contact Waste Management in the Environmental Management Department (8516) using the ES&H Hotline at 294-3724 for answers to waste questions.


11.0 REFERENCES

Requirements Source Documents

16 CFR 1500.45, Method for Determining Extremely Flammable and Flammable Contents of Self-Pressurized Containers.

29 CFR 1910, Subpart Z, Toxic and Hazardous Substances.

American Conference of Governmental Industrial Hygienists (ACGIH), 1996 TLVs® and BEIs®: Threshold Limit Values for Chemical Substances and Physical Agents, Biological Exposure Indices, Cincinnati, OH, 1996 or latest edition.

California Code of Regulations, Title 22, Social Security, Division 4.5, "Environmental Health Standards for the Management of Hazardous Waste."

DOE 5480.4, Environmental Protection, Safety, and Health Protection Standards.

International Agency for Research on Cancer (IARC), et al., ad-hoc working group on the evaluation of carcinogenic risks to humans, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, 1987.

National Toxicology Program (NTP) (see U.S. Department of Health and Human Services).

U.S. Department of Health and Human Services, Annual Report on Carcinogens, National Toxicology Program (NTP), Fifth Edition, U. S. Department of Commerce National Technical Information Service (NTIS), 1989.

Implementing Documents

ESH100.2.ENV.15, Manage Hazardous Waste at SNL/CA.

SNL, MN471000, Pressure Safety Manual.

SNL, MN471016, Radiological Protection Procedures Manual.

ESH100.2.IH.4, Evaluate and Control Chemical Hazards.

Related Documents

ANSI Z87.1A-1989, Occupational and Educational Eye and Face Protection.

Barnhard, Edward R., Physicians' Desk Reference, 2007.

Bretherick, L., Handbook of Reactive Chemical Hazards, Sixth Edition, Billing and Sons Ltd., 1999.

Bretherick, L., ed., Hazards in the Chemical Laboratory, Fourth Edition, The Royal Society of Chemistry, 1986.

Committee on Prudent Practices for Handling, Storage, and Disposal of Chemicals in Laboratories, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals, National Academy Press, 1993. Dux, J. P., and R. F. Stalzer, Managing Safety in the Chemical Laboratory, Van Nostrand Reinhold Company, Inc., 1988.

International Technical Information Institute, Toxic and Hazardous Industrial Chemicals Safety Manual, 1986.

Kaufman, J. A., Waste Disposal in Academic Institutions, Lewis Publishers, Inc., 1990.

Klaassen, C. D., M. O. Amdur, J. Doull, ed., Casarett and Doull's TOXICOLOGY: The Basic Science of Poisons, Sixth Edition, McGraw-Hill, 2001.

Lenga, R. E., ed., Sigma-Aldrich Library of Chemical Regulatory and Safety Data, Sigma-Aldrich Corporation, 1994.

Lewis, Richard J., Sr., Sax’s Dangerous Properties of Industrial Materials, Eleventh Edition, Wiley Interscience , 2000.

Lunn, G., and E. B. Sansone, Destruction of Hazardous Chemicals in the Laboratory, Second Edition, John Wiley and Sons, Inc., 1994.

Pipitone, D. A., ed., Safe Storage of Laboratory Chemicals, Second Edition, John Wiley and Sons, Inc., 1991.

Pitt, M. J., and E. Pitt, Handbook of Laboratory Waste Disposal, Ellis Horwood, Ltd., 1985.

Sax, N. I., and R. J. Lewis, Sr., eds., Rapid Guide to Hazardous Chemicals in the Workplace, Fourth Edition, Wiley-Interscience, 2000.

Shane, B. S., Human Reproductive Hazards, Environmental Science & Technology, Volume 23, Number 10, 1989.

Sitting, M., Handbook of Toxic and Hazardous Chemicals and Carcinogens, Fourth Edition, Noyes Publications, 2002.


Al Buerer, albuere@sandia.gov
Al Bendure, aobendu@sandia.gov


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