Chapter 45

CHEMICAL HYGIENE AND SAFETY PLAN

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45.7 Required Work Processes

Work Process A. General Requirements

Work Process B. Chemical and Equipment Procurement

Work Process C. Transporting Hazardous Materials

Work Process D. Berkeley Lab Chemical Inventory

Work Process E. Chemical Hazard Descriptions

Work Process F. Chemical Hazard Assessments

Work Process G. General Controls for Hazardous Materials

Work Process H. Selection and Use of Engineering Controls

Work Process I. Personal Protective Equipment

Work Process J. Work Practice Controls

Work Process K. Chemical Storage

Work Process L. Specific Controls and Procedures — Acids and Bases

Work Process M. Specific Controls and Procedures — Particularly Hazardous Substances: Carcinogens, Reproductive Toxins, and Acute Toxins

Work Process N. Specific Controls and Procedures — Flammables and Combustible Liquids

Work Process O. Specific Controls and Procedures — Laser Dyes and Solvents

Work Process P. Specific Controls and Procedures — Peroxide-Forming Compounds

Work Process Q. Specific Controls and Procedures — Water-Reactive Chemicals

Work Process R. Specific Controls and Procedures — Pyrophoric Materials

Work Process S. Specific Controls and Procedures — Engineered Nanomaterials

Work Process T. Specific Controls and Procedures — Chemicals with Explosive Properties

Work Process U. Decommissioning Equipment, Buildings, Laboratories, and Shop Spaces

Work Process V. Emergency Procedures and Equipment

Work Process W. Training

Work Process X. Hazard Information

Work Process Y. Container Labeling

Work Process Z. Hazard Communication Requirements for Chemicals Produced in Laboratories and Shipped Off Site

Work Process AA. Posting Area Entrances

Work Process BB. Designated Areas

Work Process CC. Exposure Assessments, Monitoring, and Medical Consultation

Work Process A. General Requirements

1.    Chemical Safety Work Process Flowchart

 

flowchart


2.    Employee Rights. All personnel have the right to:

a.    Be notified of measured or suspected exposures to harmful substances at or above occupational exposure limits

b.    Request medical consultations and access their workplace medical and exposure records.

c.    Refuse to work in unsafe conditions or to perform work that could create a hazard to themselves or other workers

d.    File confidential health and safety complaints with the UC Whistleblower Hotline at (800) 403-4744.            

Work Process B. Chemical and Equipment Procurement

1.    General Information. Some chemicals and equipment have inherent safety hazards that require special safety controls and authorizations. It is important that these controls are in place before the material is purchased and used on site. Several materials of concern are listed in the Restricted Items List that is maintained by the Procurement Department in consultation with EHS. The Laboratory has a notification and approval procedure for these materials that is initiated at the time of procurement.

2.    Restricted Items List

a.    The Restricted Items List includes chemicals and equipment such as:

                                          i.    Biological agents

                                         ii.    Biosafety cabinets

                                        iii.    Chemicals: lethal toxicants, unstable and reactive materials

                                       iv.    Chemical storage cabinets

                                        v.    Fire extinguishers

                                       vi.    Fume hoods

                                      vii.    Gas storage cabinets

                                     viii.    Hazardous and toxic gases

                                       ix.    Laminar airflow hoods

                                        x.    Laser equipment (excluding laser pointers)

                                       xi.    Radioactive isotopes

                                      xii.    Refrigerants and ozone-depleting substances

                                     xiii.    Refrigerators and freezers for flammable liquid storage

                                    xiv.    Respiratory protection equipment

                                     xv.    X-ray equipment

b.    Requesters, preparers, buyers, and other personnel who are responsible for purchasing materials must review the Restricted Items List and the Procurement Item Categories List to identify purchases that require EHS notification or approval. The chemical or equipment name as well as the vendor’s catalog number must be identified on the requisition and the hazardous properties of chemicals must be declared.

c.    The EHS Division reviews and approves procurement of materials such as toxic and pyrophoric gases, biological agents, selected reactive (unstable) chemicals, and respiratory protection equipment.

3.    Pre-Procurement Assessment Requirements

a.    Before receiving a hazardous material, information on proper handling, storage, and disposal must be understood. It is the responsibility of safety line management to ensure that the facilities in which the substance will be handled are adequate and that those who will handle the substance have received the proper training.

b.    The MSDS should be reviewed prior to using the substance. An industrial hygienist may also be consulted for guidance. It is also important to limit chemical purchases to the amount actually needed.

c.    Some equipment contains chemicals that can pose a hazard when mishandled, such as elemental mercury in porosimeters. When normal operation or reasonably foreseeable mishandling of equipment that contains chemicals may result in a loss of control (such as a spill) that could pose an exposure hazard, cause extensive area contamination, or result in environmental damage, the line manager must do a hazard assessment in consultation with an EHS Division subject matter expert. The using division determines if a formal authorization is needed on the basis of the risk assessment performed. Further information is provided in the ES&H Manual Safe Work Authorizations program.

Work Process C. Transporting Hazardous Materials

1.    Transporters. Hazardous materials will be transported by Transportation Services or a Department of Transportation (DOT) authorized carrier (except as outlined below). Transporting hazardous materials via public transportation (such as the shuttle bus) or in private or government vehicles is not permitted. This is to minimize risk to Laboratory employees and the public. This also ensures that the federal and state laws regarding packaging, manifesting, and placarding hazardous materials are met. There are exceptions for transporting research samples, hazardous materials, and field sampling materials, described later.

a.    The following parties are permitted to transport hazardous materials between non-adjacent Berkeley Lab buildings and from off-site locations (e.g., UC Berkeley campus):

                                          i.    Transportation Services (ext. 5404) will transport hazardous materials, provided they are unopened and still in their original DOT shipping containers. They will also transport gas cylinders. In addition, Berkeley Lab Transportation Services will package and label hazardous materials in accordance with DOT Title 49 regulations for shipment by commercial carriers.

                                        ii.    MSDSs and hazard warning labels are required for off-site shipments of chemicals that are created or synthesized at Berkeley Lab. Refer to Appendix A of this program for additional information on MSDSs.

                                        iii.    The EHS Waste Management Group (ext. 5877 ) will transport hazardous materials that have previously been opened. This is normally needed for laboratory moves.

                                       iv.    Facilities craft personnel will transport paints, solvents, cleaners, and other materials necessary to perform their work.

2.    Transporting Small Quantities of Hazardous Materials by Laboratory Employees, Subcontractors, and Affiliates

a.    Laboratory employees, subcontractors, and affiliates may move small quantities of hazardous materials for short distances within a building or between adjacent buildings, provided it can be done safely and without spilling the materials. Individuals must use handcarts and drip trays (to contain any spilled material). Employees must also complete Chemical Hygiene and Safety Training (EHS0348; or 345 for Facilities personnel or 352 for summer students). Use standard cylinder dollies to transport compressed gas cylinders. While dollies are preferred, cylinders weighing 11 kg (25 lbs) or less may be hand-carried.

b.    Never move a cylinder with a regulator connected to it. Cylinder valve-protection caps and valve-opening caps must be in place when moving cylinders. Lecture bottles and other cylinders not normally equipped with valve-protection caps should be transported in either the original DOT specification package or an equivalent container.

c.    NOTE: Contact an EHS Radiological Control Technician for guidance on transporting radiological isotopes.

3.    Transporting Research Samples, Hazardous Materials, and Field Sampling Materials by Berkeley Lab Staff

a.    Policy and Procedures

                                          i.    The policy for transporting research samples, hazardous materials, and field sampling materials by Berkeley Lab staff is established in the ES&H Manual Transporting and Shipping Hazardous Materials program. The process described below is the procedure for implementing this policy.

                                         ii.    Berkeley Lab staff (i.e., anyone with a Berkeley Lab badge) may transport research samples and small quantities of hazardous materials by hand or in a passenger vehicle under the conditions defined by procedures described below. “Small quantities” is defined in the Scope and Application section below. A research sample is a material used or developed in a laboratory for research purposes, for further use, study, analysis, or characterization.

                                        iii.    Shipping samples and hazardous materials by common carrier (FedEx, UPS, USPS) to off-site locations must be done by Facilities Material Services. This is addressed in Work Process E, Shipping, of the Transporting and Shipping Hazardous Materials program in the ES&H Manual.

                                       iv.    Questions regarding this policy may be addressed to the EHS Deputy for Technical Programs.  

4.    Scope and Application

a.    This policy applies to Berkeley Lab staff who:

                                          i.    Transport research samples (including engineered nanomaterials) and hazardous chemicals between:

i.         Non-adjacent buildings at the main Berkeley Lab site

ii.        The main Berkeley Lab site and other Laboratory sites (e.g., Donner, Potter, JBEI, JGI)

iii.      Any Berkeley Lab site and other collaborating research organization (e.g., UC Berkeley and Stanford)

                                         ii.    Transport small quantities of hazardous materials to and from field locations not readily served by common carriers such as FedEx and UPS.

b.    This policy applies to research samples and hazardous materials in the following DOT hazard categories. These materials must be contained in proper packaging (see below) and shall not exceed 0.5 kg (1 lb) or 0.5 L (1 pint) gross packaging size. To determine hazard class, consult a Material Safety Data Sheet (MSDS) or contact the EHS Transportation Subject Matter Expert (ext. 4826).

                                          i.    Class 3 (flammable liquid)

                                         ii.    Class 8 (corrosive material)

                                        iii.    Class 9 (other regulated material)

                                       iv.    Division 4.1 (flammable solid)

                                        v.    Division 5.1 (oxidizer)

                                       vi.    Division 5.2 (organic peroxide)

                                      vii.    Division 6.1 (toxic or poisonous)

                                     viii.    ORM-D (other regulated material, consumer commodity)

c.    Contact the EHS Deputy Division Directorfor exemptions to the above hazard class/quantity limitations, or for transporting materials in the following DOT hazard categories:

                                          i.    Division 2.1 (flammable gas)

                                         ii.    Division 2.2 (nonflammable gas)

5.    Prohibitions. This policy does not apply to biological materials and materials that are radioactive, self-reactive, pyrophoric, explosive, water-reactive, acutely toxic by inhalation, or a hazardous waste. "Acutely toxic" refers to substances that may be fatal or cause damage to target organs from a single exposure or from exposures of short duration. It also includes materials capable of causing intense irritation that can result in pulmonary edema (fluid and swelling in the lungs), chemical asphyxia, and systemic (body-wide) poisoning. A substance's acute toxicity may be determined by consulting a Material Safety Data Sheet. Contact the EHS Transportation Subject Matter Expert for further information.

6.    Personnel Qualifications

a.    Staff transporting hazardous materials must have Chemical Hygiene and Safety Training (EHS0348), Chemical Hygiene and Safety Refresher Training (EHS0353) as applicable, and Safe Handling of Engineered Nanoscale Particulate Matter (EHS 0344) if they transport engineered nanoscale particulate matter. Employees’ Job Hazards Analyses (JHAs) must note that they transport research samples and small quantities of hazardous materials.

b.    Facilities Material Services personnel who package materials for common carrier shipment must be qualified in accordance with the DOT or the International Air Transport Association (IATA) regulations.

7.    Packaging Requirements for Hand Carrying and Transportation by Vehicle

a.    An inner receptacle and outer packaging are required (see photos below):

b.    Containers can be procured from a variety of companies such as Grainger (formerly called Lab Safety Supply) or HAZMATPAC, Inc.

Inner receptacle with positive closure and label

inner receptacle

Ziplock bag to contain leaks/spills
ziplock bag

Outer packaging
Outer packaging


c.    The inner receptacle must be:

i.         Leak-tight, securely closed, and protected against damage. A screw-type cap or other positive means of closure is required. Parafilm, aluminum foil, and stoppers are prohibited.

ii.        Labeled with the identity of the material, its hazard, the name and phone number of the sender, and the name and phone number of the recipient (if different from the sender). The chemical identity must be the common name or the DOT proper shipping name. Chemical formulas, abbreviations, or acronyms are prohibited. If the material is an engineered nanomaterial, include the following words on the label:

“Nanoscale — This material’s toxicity, reactivity, and
other hazards may be greater than its macro-size forms”

iii.      Placed in a ziplock bag or equivalent to serve as secondary containment in the event of a leak

iv.      Sealed in an outer package

d.    The outer packaging must:

i.         Be made of rigid material such as a cardboard or plastic, or a metal box or pail

ii.        Contain cushioning material to prevent breakage and to maintain each inner receptacle in an upright condition

iii.      Have the same labeling as the inner receptacle

iv.      Note: multiple chemicals in the same outer package must be chemically compatible with each other.

8.    Communication of Chemical Hazards in Transport

a.    Staff transporting material must inform vehicle passengers about the research samples/hazardous materials being transported and the requirements of this policy.

b.    If a substance is produced for use by another person, a Material Safety Data Sheet must be developed and placed inside the outer package. 

9.    Other Requirements for Staff Hand-carrying and Transporting by Vehicle

a.    Maintain possession and control of the material at all times.

b.    Transport the material directly to its final destination with no intermediate stops.

c.    Using Berkeley Lab shuttle buses and other modes of public transit is prohibited.

d.    Keep hazardous materials in the car trunk or truck bed. Do not transport in the passenger compartment.

e.    Use a DOT- or OSHA-approved safety can with a rated volume of 5 gallons or less to transport gasoline to field locations. Keep it in the open bed of a truck. Do not transport in the trunk or compartment of a passenger vehicle.

f.     DOT placarding is not required for vehicles provided that the quantity and classification criteria described in Scope and Application (above) are followed.

g.    Keep purchased materials intended for field use in the manufacturer’s original packaging. Otherwise, follow the packaging requirements as describe above.

h.    Update the Chemical Management System (ext. 2994) for applicable containers moved to another location. 

10. Requirements for Shipping by Common Carrier

a.    The OSHA Hazard Communication standard (29 CFR 1910.1200) requires MSDSs and container labeling for research samples and hazardous chemicals that are shipped from laboratories. There is no exemption based on size or volume. start flag Consult Work Process Z, Hazard Communication Requirements for Chemicals Produced in Laboratories and Shipped Off Site, for hazard communication requirements.end flag Berkeley Lab also requires adherence to Work Process E, Shipping, of the Transporting and Shipping Hazardous Materials program in the ES&H Manual. Only qualified individuals in Facilities Material Services (ext. 5084) may pack and ship these materials off site. Berkeley Lab employees intending to send research samples and hazardous materials off site must:

                                          i.    Label the material as described in Work Process C, Hand-Carrying or Self-Transport by Hand and Foot; and Work Process D, Self-Transport by Vehicle, of the Transporting and Shipping Hazardous Materials program. Also list the sender’s address.

                                         ii.    Prepare an MSDS to be shipped with the material. Consult the Berkeley Lab Chemical Hygiene and Safety Plan Program Manager (ext. 5286) for guidance.

                                        iii.    Coordinate pickup with Facilities Material Services (ext. 5084).

                                       iv.    Notify the recipient via e-mail prior to transport. Maintain a copy of the e-mail.

b.    Facilities Material Services shall:

                                          i.    Arrange for pickup of the material

                                         ii.    Pack the material in accordance with DOT and/or IATA regulations

Work Process D. start flag Berkeley Lab Chemical Inventory end flag

1.    Purpose

a.    The purpose of the site-wide chemical inventory is to provide chemical users, EHS staff, and emergency response teams with accurate and up-to-date lists of chemicals stored on site. Furthermore, OSHA requires that a chemical list be maintained. Current chemical inventory reports must also be provided for compliance with DOE and city of Berkeley regulations. The inventory is also used to categorize chemicals into their respective hazard classes and to use this information as a tool to:

                                          i.    Identify users of particular materials

                                         ii.    Communicate hazard information, including special controls or procedures

                                        iii.    Assist EHS in helping chemical users to determine if exposure assessments are needed

b.    Use of the chemical inventory permits emergency personnel to respond to unplanned releases with appropriate training, equipment, and organizational support. A well-maintained chemical inventory can also aid in internal Laboratory management of business and research needs.

2.    Responsibilities

a.    The EHS Division hosts the site-wide chemical inventory database within the Chemical Management System.

b.    All hazardous materials are required to be included in the Chemical Management System (CMS). MSDSs for materials should be consulted to determine hazard status. An EHS industrial hygienist may be consulted to help determine the hazards of a chemical or product.

3.    Chemical Owners

a.    A chemical owner is accountable for the safe storage of hazardous chemicals, though all chemical users share the responsibility to use and store hazardous materials safely. Safe chemical usage is a Line Management responsibility.

b.    A chemical owner must provide the resources to make safe storage possible. This includes the purchase of equipment and accessories — such as cabinets and storage containers for flammables and corrosives — to control hazards. The chemical owner must have the authority to set administrative controls such as procedures for safe storage of chemicals. Guests, students, visiting scientists, and other short-term staff usually do not meet these requirements, but it is up to each division to assign ownership of chemicals and hazardous materials.

4.    Chemical Management System (CMS)

a.    The chemical owner must ensure that all hazardous chemicals/materials for which he or she is responsible are entered into the CMS as soon as possible and that all chemicals are removed from or disposed of in the inventory when the materials have been used up, disposed of, or taken off site.

b.    The CMS identifies containers (or groups of identical containers) with a barcode containing a six-digit ID number. The barcode should be affixed to the container with the ID number completely visible, in the case of small containers. The barcode should be attached vertically to facilitate electronic scanning. Container barcodes appear in pairs; one barcode should be affixed to the container and one to a chemical inventory data sheet. Barcodes can be obtained through chemical management at ext. 2994, CMS@lbl.gov.

c.    The following information must be added to the CMS for each chemical:

                                          i.    Container barcode (ID number)

                                         ii.    Chemical or product name

                                        iii.    Container size

                                       iv.    Container unit (kg, l, ml, etc.)

                                        v.    Container type (glass bottle, can, etc.)

                                       vi.    Physical state (solid, liquid, gas)

                                      vii.    Manufacturer

                                     viii.    Temperature

                                       ix.    Pressure

                                        x.    Building

                                       xi.    Room

                                      xii.    Owner

d.    Note: When entering groups of materials or materials with a high throughput rate (such as commonly used organic solvents, acids, and bases), a CMS record can represent multiple identical containers in CMS. In such cases, the maximum amount possible should be indicated in the Size/Unit of the record. Contact Chemical Management System Support at CMS@lbl.gov for information on inventory implementation and training.

5.    Content Guidance

a.    All hazardous materials/chemicals must be entered into the database, with the following exceptions:

                                          i.    Biochemical materials such as cell-culture media, amino acids, or lipids that have been determined to be nonhazardous using available health and safety information.

                                         ii.    Research-produced chemicals and mixtures

                                        iii.    Chemicals or chemical products transferred to secondary (nonmanufacturer) containers

                                       iv.    Radiological materials

                                        v.    Chemicals transferred to waste containers

                                       vi.    Individual components of prepackaged chemical kits (see below)

                                      vii.    Secondary containers. These are jars, cans, squeeze bottles, and other containers to which hazardous materials are transferred from the original container by an individual.

                                     viii.    Consumer products, which can be excluded from the CMS if their usage is consistent with how the manufacturer intends the average consumer to use the product. Example: Bleach that is used infrequently for cleaning can be excluded. However, bleach that is used daily for work tasks such as disinfecting work surfaces in a tissue-culture laboratory is beyond what is considered average consumer usage as intended by the manufacturer and must be entered into CMS.

b.    All consumer adhesives and sealants must be inventoried.

c.    Mixtures

                                          i.    The chemical name and concentration fields should be filled with data on the most hazardous component (consult MSDS), while the remaining components and respective concentrations should be entered into the comment field. The following are examples of how various mixtures should be entered into the database:

1.    Aqueous solutions such as nitric acid or sodium chloride and their concentrations (or molarities) should appear in their respective fields. The concentration of water in a solution is assumed to complete the mixture.

2.    Gas mixtures, such as 2000 ppm of hydrogen in argon, are entered as “Hydrogen” with “2000 ppm” in the concentration field. Inert gases should be entered in the comment.

d.    Consumable materials such as grinding wheels, welding rods, or solder material that can be used up, dispersed, or aerosolized during use must be entered into the CMS.

e.    Prepackaged kits that are sets of chemical components intended for use for a specific task, test, or procedure, must be entered into the CMS. NOTE: Individual components do not need to be entered individually. The kit may be entered as a whole, identified by the name as it appears on the manufacturer’s MSDS.

f.     Multicontainer Data Sheets 

                                          i.    These can be used for groups of identical containers in lieu of barcoding individual items. These sheets must be posted and clearly visible when the container represented is visible. The number of containers represented by the barcode on a multicontainer data sheet must be clearly identified. If the number of identical containers varies, a max amount possible should be identified (and should not be exceeded at any time).

                                         ii.    Exception: California and DOE regulations on the use of greenhouse gases require Berkeley Lab to report amounts annually. This multicontainer option does not apply to greenhouse gases such as sulfur hexafluoride (SF6). All greenhouse gases such as SF6 must be individually entered into the CMS to enable accurate reporting.

                                        iii.    Examples of multicontainer data sheets in use:

Situation

Multicontainer Data Sheet

Gas cylinder storage area with:

·         Five cylinders of 100% methane

·         Two cylinders of 2% hydrogen /helium balance (possibility of up to 4% H/He mix)

Sheet is posted clearly above gas storage racks:

·         One barcode represents five cylinders of methane

·         Separate barcode represents four cylinders of H/He mix

Flammables storage cabinet containing:

·         Three 4-liter bottles of acetone

·         Six 1-1iter bottles of methanol

Sheet is posted on the outside of the flammables cabinet:

·         One barcode for acetone

·         Separate barcode for methanol

Advanced Usage!

·         Room 100 contains four cylinders of methane.

·         One cylinder is taken to Room 200 every week for use and returned for storage.

Two separate sheets with two separate barcodes are posted:

·         One in Room 100 listing four cylinders

·         One in Room 200 listing one cylinder

Using this method, one cylinder can be moved from Room 100 to Room 200 and back as often as needed without the need to update CMS to reflect the change in room.

g.    Accessing CMS

                                          i.    CMS on the Web can be accessed at cms.lbl.gov. Log on using your LDAP (same as e-mail) user name and password.

                                         ii.    Please contact CMS Support at ext. 2994 or CMS@lbl.gov for database access and information regarding roles and responsibilities.

Work Process E. Chemical Hazard Descriptions

*     This section provides resources and information that can be used to evaluate the hazards of chemicals. The terms used in this section are listed in the Definitions section. The OSHA Hazard Communication standard defines a hazardous chemical as a chemical that is either a health hazard or a physical hazard.

1.    Health Hazard. A "health hazard" is 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 that are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, hepatotoxins (liver toxins), nephrotoxins (kidney toxins), neurotoxins, agents that act on the hematopoietic (blood-forming) system, and agents that damage the lungs, skin, eyes, or mucous membranes.

2.    Physical Hazard. A chemical is a physical hazard if it has flammable, combustible, explosive, oxidizing, pyrophoric, or reactive (including water-reactive) properties, or if it is an organic peroxide or compressed gas.

3.    Information and Resources. The following sources of information may be used to determine the hazards of chemicals:

a.    Material Safety Data Sheets: MSDSs list both health and physical hazards of chemicals.

b.    OSHA 29 CFR 1910.1000 Subpart Z, Toxic and Hazardous Substances: Subpart Z has a list of hazardous chemicals and their respective airborne permissible exposure limits.

c.    Threshold Limit Values for Chemical Substances and Physical Agents in the Work Environment, American Conference of Governmental Industrial Hygienists (ACGIH),  latest edition: Includes a list of hazardous chemicals and their respective airborne occupational exposure limits.

d.    Micromedix Tomes CPSTM: A compendium of several toxicological databases.

e.    International Agency for Research on Cancer (IARC): Evaluates the carcinogenicity of chemicals and ranks their carcinogenic potential. Chemicals with IARC classifications of 1, 2A, and 2B are considered by OSHA to be carcinogenic.

f.     National Toxicology Program (NTP) biennial Report on Carcinogens, latest edition: Chemicals with NTP classifications of A or B are considered by OSHA to be carcinogenic.

g.    National Institute for Safety and Health (NIOSH) Pocket Guide to Chemical Hazards: Presents the health and physical hazards of chemicals.

h.    The Registry of Toxic Effects of Chemical Substances (RTECS), National Institute for Occupational Safety and Health NIOSH (latest edition)

i.      An EHS industrial hygienist may also be consulted to assist in evaluating chemical hazards. end flag

4.    Mixtures

a.    Many products used in the workplace are mixtures of different chemicals. In accordance with OSHA, a mixture is assumed to present the same health hazards as each component that comprises 1% or more of the mixture. A mixture is assumed to be carcinogenic if it contains a carcinogenic component in a concentration of 0.1% or more.

b.    The Chemical Toxicology Overview in Appendix B of this program has additional information on the health effects of chemicals.

5.    Particularly Hazardous Substances

a.    OSHA established a category of chemicals known as particularly hazardous substances for which additional precautions beyond standard operating procedures may be required. Particularly hazardous substances include select carcinogens, reproductive toxins, and substances with a high degree of acute toxicity.

b.    Work leads are responsible for work involving particularly hazardous substances and must ensure that proper controls are in place and that area-specific training is given. An EHS industrial hygienist may be consulted to provide assistance. For some work, an Activity Hazard Document may be required. Work Process M, Specific Controls and Procedures — Particularly Hazardous Substances: Carcinogens, Reproductive Toxins, and Acute Toxins, provides additional information for the identification and control of these chemicals.

6.    Engineered Nanomaterials

a.    Engineered nanomaterials are:

                                          i.    Discrete materials having structures with at least one dimension between 1 and 100 nanometers (nm)

                                         ii.    Intentionally created, as opposed to naturally or incidentally formed

b.    Engineered nanomaterials do not include:

                                          i.    Larger materials that may have nanoscale features, for example etched silicon wafers.

                                         ii.    Biomolecules (proteins, nucleic acids, and carbohydrates)

                                        iii.    Materials with occupational exposure limits (OELs) that address nanosize particles for that substance

c.   start flag Unbound engineered nanoscale particles (UNP) are defined as nanoscale particles that are not contained within a matrix under normal temperature and pressure conditions that would reasonably be expected to prevent the particles from being separately mobile and a potential source of exposure.

                                                              i.      An engineered primary nanoscale particle dispersed and fixed within a polymer matrix, incapable as a practical matter of becoming airborne, would be “bound,” while such a particle loosely attached to a surface (e.g., nanowire forest grown on wafer) or suspended in liquid (e.g., nanoparticles in colloidal suspension) or a dry powder would be “unbound.” end flag

                               d.    Exposures to these materials may occur through inhalation, dermal contact, or ingestion. Animal studies indicate that low-solubility ultrafine particles may be more toxic than larger ones on a mass-for-mass basis. Because of their tiny size, they can penetrate deep into the lungs and may translocate to other organs following pathways that have not been demonstrated in studies with larger particles. In addition, the nanoparticulate forms of some materials show higher reactivity, especially for fire, explosion, and in catalytic reactions.

7.    Consumables. start flagConsumables are materials such as solder, welding rods, and grinding wheels. These are considered hazardous materials because they may produce airborne dust, fumes, or particulates when used in the manner intended by the manufacture. Wood is also considered as a hazardous material if it is cut or sawn to produce airborne dust. end flag

Work Process F. Chemical Hazard Assessments

1.       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 EHS professional. Hazard assessments may precede Exposure Assessments (Work Process CC), which are conducted by EHS professionals to ensure that protective measures are implemented and 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 ES&H Manual Exposure Assessment program.

2.       ISM. In accordance with Integrated Safety Management (ISM) principles, work leads are responsible for “integrating EHS 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.

3.       Authorization. All work performed at Berkeley Lab must be authorized by safety line management. The Laboratory protocol for determining the proper level of work authorization is delineated in the ES&H Manual Safe Work Authorizations program. The ultimate determination of the appropriate work authorization is the responsibility of the principal investigator (PI) or the supervisor for that work.

4.       Job Hazards Analysis (JHA)

a.    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 JHA process is given in ES&H Manual Job Hazards Analysis program. All work at Berkeley Lab must be authorized through the JHA. Work may not be performed until the JHA is complete, the work is authorized by the work lead, and the proper controls as specified by the JHA are in place.

b.    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 EHS 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.

5.       Activity Hazard Document

a.    OSHA mandates that employers identify higher hazard work that requires prior approval. At Berkeley Lab, this is accomplished with the Activity Hazard Document (AHD).

b.    An AHD is a formal work authorization that 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.

c.    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.

d.    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 EHS health and safety professionals and line management.

e.    Work under an AHD is authorized by the responsible division director with EHS concurrence.

f.     The Berkeley Lab protocol for determining the proper level of work authorization is delineated in ES&H Manual Safe Work Authorizations program.

g.    All AHDs are developed, reviewed, and approved through the Laboratory’s Activity Hazard Document Database. Examples of activities requiring AHDs include:

                                          i.    Activities requiring the use of glove boxes for safety reasons

                                         ii.    Work that uses toxic or pyrophoric gases (ES&H Manual Gas Safety program), may be consulted for further guidance on controls for toxic and pyrophoric gases; see List of Toxic/Pyrophoric Gases, below)

                                        iii.    Activities that involve reactive or explosive chemicals (See Section 7, List of Reactive and Explosive Substances, below).

                                       iv.    Work that uses chemicals possessing lethal or incapacitating toxicity or chemicals that have an LD50 of 0.5 mg/kg or less (see Section 8, List of Chemicals Possessing Lethal or Incapacitating Toxicity, below).

                                        v.    Other activities with chemicals for which an EHS industrial hygienist determines that an AHD is required.

h.    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) to determine hazardous properties of chemicals:

6.       List of 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

7.       List of 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

8.       List of Chemicals Possessing Lethal or Incapacitating Toxicity

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]   

9.       The following chemicals also exhibit toxic properties of concern. An EHS 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]

10.    If there is any uncertainty regarding the need to develop an AHD for work involving chemicals, the work lead must contact an EHS industrial hygienist for guidance.

Work Process G. General Controls for Hazardous Materials

This work process discusses control procedures for limiting employee exposure to chemical hazards.

1.       Standard Operating Procedures. Standard operating procedures for all chemicals at Berkeley Lab minimize employee exposure to hazards by using chemical substitution, engineering controls, administrative controls, personal protective equipment, work practice controls, and emergency procedures, all of which described in this section. All employees are required to wear eye protection, lab coats, and chemically resistant gloves when handling hazardous chemicals. Operations that may generate airborne gases, vapors, dusts, fumes, and smoke must be done in a fume hood or glove box. In addition, specific controls for the following classes of hazardous materials are described in more detail below. Work leads shall incorporate the controls discussed in this section into JHAs and AHDs.

a.    Acids and Bases (Work Process L)

b.    Particularly Hazardous Substances (Work Process M)

                                          i.    Carcinogens (Work Process M.1)

                                         ii.    Reproductive Toxins (Work Process M.2)

c.    Flammables and Combustible Liquids (Work Process N)

d.    Laser Dyes and Solvents (Work Process O)

e.    Peroxide-Forming Compounds (Work Process P)

f.     Water-Reactive Chemicals (Work Process Q)

g.    Pyrophoric Materials (Work Process R)

h.    Engineered Nanomaterials (Work Process S)

i.      Chemicals with Explosive Properties (Work Process T)

2.    Chemical Use, Selection, and Substitution. Before a chemical or a product is introduced or used in a workplace, the work lead must:

a.    Review the hazards of the material and assess the conditions under which it will be used. This information may be obtained from the MSDS or by consultation with EHS industrial hygienists.

b.    Determine whether the chemical can be substituted with a safer chemical alternative. An EHS industrial hygienist can be consulted to provide assistance to identify substitute chemicals.

c.    Determine whether the chemical can be borrowed from someone within the research group or the division. If the chemical must be purchased, keep working quantities of all hazardous materials to a minimum. Procure, use, and store the minimum amount of material required.

d.    Determine whether the chemical is a restricted item. If it is, notification or approval must be obtained from the EHS Division in accordance with the Laboratory's procurement requirements.

 

NOTE: When a chemical is synthesized or produced at Berkeley Lab and is to be used by someone outside the Laboratory or research group where it was produced, an MSDS and warning label must be generated. See MSDSs for additional requirements (see Appendix A of this program for information about MSDSs). If the chemical is to be used in the laboratory, the work lead shall conduct a hazard assessment, identify the hazards, establish controls, label the container, and provide training to the users.

Work Process H. Selection and Use of Engineering Controls

Engineering controls include local exhaust ventilation systems, laboratory fume hoods, enclosures, and shields. Except for substitution, these provide the most effective means of control because they enclose the hazard or physically separate it from the employee.

1.    Local Exhaust Ventilation, Fume Hoods

fume hood

a.    Local exhaust ventilation and laboratory fume hoods are used to remove airborne contaminants from an employee's breathing zone. Self-contained (ductless) hoods that recirculate air back into the workspace are not an acceptable means to control airborne chemicals. Berkeley Lab policy on selecting, installing, using, and testing ventilation systems is provided in the ES&H Manual Industrial Hygiene program. The selection, procurement, installation, and balancing of all ventilation systems must be done through Facilities.

glove box

b.    Local exhaust ventilation (such as laboratory fume hoods, glove boxes, “snorkels,” or industrial ventilation) is required when handling chemicals in a manner that can produce an airborne hazard. 

c.    Examples of activities requiring local exhaust ventilation include but are not limited to:

                                          i.    Using reactive metals or pyrophoric materials

                                         ii.    Using particularly hazardous substances (i.e., acutely toxic, carcinogenic, or reproductive toxins)

                                        iii.    Handling volatile toxic liquids

                                       iv.    Using organic liquids or solvents

                                        v.    Conducting procedures that generate airborne particulates (e.g., dust) or liquid aerosols of even moderately toxic chemicals

                                       vi.    Using odiferous compounds

                                      vii.    Synthesizing or reacting chemicals

                                     viii.    Diluting concentrated acids and bases. NOTE: Operations involving heating or evaporating perchloric acid must be evaluated by an EHS industrial hygienist to determine whether special controls (such as using an acid fume hood with wash-down systems to prevent the accumulation of explosive perchlorate crystals) are needed

                                       ix.    Discharging gases/vapors from vacuum pumps and distillation columns

                                        x.    Discharging harmful gases and vapors from drying ovens and muffle furnaces; NOTE: Consult an industrial hygienist to help make this determination.

d.    Fume hoods, gas cabinets, and other ventilated enclosures may be equipped with electronic flow sensors or pressure gauges. If the flow sensor alarm goes off (red light, warning sound) or the pressure falls below the indicated set point on the pressure gauge, discontinue work in that system and call the Work Request Center (ext. 6274; for after-hours emergency service, call ext. 5481) to report the condition. Do not simply mute the alarm and continue working — the alarm indicates that something is not operating correctly. If the system is restored and the alarm resets, you may resume work, but you should report the condition so that the cause may be investigated.

2.    Glove Boxes and Gas Cabinets

a.    Glove boxes that provide a nonreactive atmosphere are required for operations involving alkali metals and pyrophoric materials.

b.    Gas cabinets are required for health-hazard and pyrophoric gases as described in ES&H Manual Gas Safety program. NOTE: Fume hoods may be used for this purpose as well, based upon Industrial Hygiene review and concurrence.

3.    Chemical Storage Cabinets

a.    New chemical storage cabinets (such as storage lockers for flammable liquids) must be connected to the building’s exhaust system. This applies to all cabinets installed during renovation or new construction. Most chemical storage cabinets are equipped with two bungs. It is Berkeley Lab policy to connect the bottom bung to the exhaust system with a metallic pipe (copper or steel flex hose of 2-inch diameter). The top bung must be connected to a source of non-laboratory supply air and must be fitted with a flame arrester.

b.    Existing cabinets showing signs of interior corrosion or whose contents produce strong odors during storage shall also be ventilated.

4.    Laboratory Room Exhaust. Laboratory heating, ventilating, and air conditioning (HVAC) systems must provide 100% outside air to laboratory spaces (no recirculation of air is allowed). The HVAC systems are balanced to keep laboratory spaces at a negative pressure relative to adjacent offices and hallways. This ensures that vapors, gases, fumes, and particulates do not migrate to nonlaboratory spaces. A minimum ventilation rate of 1 cubic foot per minute of exhaust per square foot of laboratory area is required. Exceptions to maintaining negative pressure in a laboratory can be made provided that it can be demonstrated that research is adversely affected by ambient air drawn into the workspace and that EHS industrial hygienist concurrence is given.

5.    Ventilation System Performance Evaluations

ventilation system

a.    Facilities is responsible for installing, balancing, and function testing all ventilation devices.

b.    EHS industrial hygienists perform periodic testing of fume hoods, gas cabinets, glove boxes, canopy hoods, and snorkels. These are evaluated initially after installation. Ventilation devices with no visual/audible readout/alarm for the airflow are also tested annually. Those equipped with visual/audible readout/alarms for airflow are evaluated every other year. Ventilation devices used for radiological work are evaluated annually.

c.    Ventilation system performance must be checked whenever the system has been modified, such as by adding new hoods or relocating or replacing system components (including hoods).

6.    Safety Shields. Safety shields must be used for protection against possible explosions or uncontrolled reactions. Laboratory equipment must be shielded on all sides to ensure there is no line-of-sight exposure of personnel.

Work Process I. Personal Protective Equipment

Personal protective equipment (PPE) is to be used as a supplement to but not as a substitute for engineering controls. PPE includes chemically resistant gloves, eyewear, footwear, lab coats, aprons, coveralls, and respiratory protection. PPE may be used as a sole means of control if the use of other controls is not feasible. PPE is provided at no personal expense to the individual. To be effective, employees must understand the proper selection, use, and limitations of PPE. For additional information on Berkeley Lab's policies on PPE, see the ES&H Manual Personal Protective Equipment program.

1.    General PPE Requirements

ppe

a.    Skin and eye contact must be prevented. PPE must be selected on the basis of the hazards present, the type of materials used, and the manner in which they will be handled. Work leads are responsible for ensuring that a Job Hazards Analysis is performed prior to selecting PPE and for ensuring that employees use PPE properly.

b.    Employees must be trained in the uses and limitations of PPE. This is the work lead's responsibility. An industrial hygienist may be consulted to provide guidance on the selection and use of PPE and to assist in training.

c.    Employees must report problems (such as deterioration and degradation) to work leads immediately.

2.    Removing PPE

a.    Remove lab coats, coveralls, and gloves prior to leaving technical areas (labs, workrooms, and similar areas) when going to common areas such as lunchrooms, conference rooms, offices, restrooms, and the cafeteria.

b.    Remove gloves before touching common use items such as phones, computers, light switches, and doorknobs.

c.    Remove lab coats, coveralls, and gloves used for protection against engineered nanomaterials before leaving the area, regardless of your destination.

d.    The above requirements also apply to technical areas where biological materials are used.

3.    Disposing of PPE

a.    Normally, disposable PPE used in laboratory settings (such as gloves, Tyvek coveralls, and booties) may be disposed of as regular trash. However, PPE used for protection against materials such as engineered nanomaterials, lead, and asbestos must be disposed of as hazardous waste. Consult with an EHS Waste Generator Assistant for more information.  

b.    Consult with a radiological control technician for disposing of PPE used in radiological areas.

c.    Dispose of PPE used for protection against biological materials in accordance with Berkeley Lab medical waste management procedures.

4.    Minimum PPE Requirements

a.    Area PPE Requirements

                                         i.    Area PPE requirements must be established for all technical areas. This is the responsibility of the area safety leader through consultation with supervisors and work leads.

                                        ii.    Area PPE requirements must be listed on the Berkeley Lab entrance placard.

                                       iii.    Area PPE requirements apply to the entire technical area unless an exception is granted in accordance with the procedure described in Appendix A, PPE and Food/Drink Requirements and Responsibilities Table, of the Personal Protective Equipment (PPE) program in the ES&H Manual.

b.    Minimum Area PPE requirements for technical areas are as follows:

                                         i.    Safety glasses with side shields

                                        ii.    Closed-toe shoes

                                       iii.    Long pants

c.    Note: Until March 1, 2009, if the policy above is not implemented and followed, the following, prior policy, must be followed:

                                         i.    The Laboratory requires suitable equipment to protect employees from hazards in the workplace as prescribed in 29 CFR 1910.132. The EHS Division advises on the protective equipment required for a task, but the supervisor of the operation must obtain this equipment and see that it is used.

                                        ii.    Visitors and persons walking through a technical area but not performing work in that area must wear the minimum Area PPE, but generally are not required to wear additional PPE assigned on the basis of performing operations.

5.    Gloves

gloves

a.    Gloves must be worn when using hazardous chemicals, when handling materials at temperature extremes, or when handling materials with sharp or rough surfaces. It is especially important to wear gloves when handling chemicals that can be absorbed through the intact skin. Consult MSDSs and the OSHA Occupational Chemical Database at https://www.osha.gov/chemicaldata/ to identify chemicals that have this property. This may not be a complete list; therefore, contact an EHS industrial hygienist if you have any questions about a particular compound.

b.    Store gloves in a clean area outside of fume hoods and away from equipment that could potentially contaminate them.

c.    Always remove gloves before touching common use items such as phones, doorknobs, and computers. This will prevent contamination of unprotected individuals.

d.    Glove Selection

                                         i.    Chemically resistant gloves are manufactured from a variety of materials, including nitrile, polyvinyl chloride, natural rubber (latex), and Viton. No single glove material provides universal protection against all chemical agents. Therefore, gloves must be selected on the basis of their resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes.

                                        ii.    Improper selection may degrade the gloves, allow the chemical to permeate through the gloves, and ultimately expose the wearer to the chemical. This is a potentially serious situation. Use chemical resistance charts and glove selection databases (below) to choose gloves.

                                       iii.    In addition to the specific chemical(s), other factors to consider in selecting gloves are how and where they will be used. In shop environments, gloves may be subjected to rougher handling and may be totally immersed in chemicals such as cleaners and degreasers. In labs, manual dexterity may be an issue; splashes, as opposed to total immersion in the chemical, are more common. Gloves used in shop settings are thus required to be more resistant to tears and abrasion than those used in laboratory environments and are normally thicker (greater than 10-15 mils). In laboratories, thin, lightweight gloves are generally preferred (less than 10 mils). As a point of reference, typical dishwashing gloves are approximately 15 to 20 mils thick, and surgical latex gloves are on the order of 3 to 8 mils thick.

                                      iv.    A final consideration in glove selection is an individual’s sensitivity to the materials and chemicals used in the manufacture of gloves. Some people have allergic reactions to natural rubber proteins in latex, glove powder (used for absorbing perspiration), or other chemical constituents, such as rubber accelerators (carbamates, thiurams, and mercaptobenzothiazole).

e.    Chemical-Resistance Charts and Glove-Selection Databases

                                         i.    Objective data (such as chemical-resistance charts and selection databases) must be used to choose the appropriate glove. Chemical-resistance charts are available from the Laboratory’s Chemical Hygiene and Safety Program Manager (ext. 5286) or directly from the manufacturer.

                                        ii.    The Web sites listed below are recommended for selecting chemically resistant gloves. Some allow different ways to search for the most appropriate glove. Searching by chemical name will produce a list of gloves that protect against a particular agent. Searching by glove type will give a list of chemicals for which a specific glove was tested. Glove thickness is normally listed or is available by clicking on the link for the recommended glove.

1.    Glove Manufacturer Web Sites:

·         start flagSpecWare Online Chemical Hand Protection

·         ChemRest Guide to Chemical Resistant Gloves

·         MAPA Chemical Resistance Guideend flag

2.    Independent Glove Selection Web Sites:

·         Michigan State University Chemical-Resistant Glove Guide

·         Oklahoma State University Chemical Guide and Permeation Tables

3.    An EHS industrial hygienist may also be contacted for assistance in glove selection.

6.    Eye and Face Protection. This section discusses the uses and limitations of safety glasses, chemical goggles, and face shields. The type of protection selected must be based on risk — i.e., the degree of hazard (severity) and the likelihood of an accident occurring (probability).

eye/face protection

 

a.    All eye and face protection must meet the Basic Impact Testing Requirements of the latest version of the American National Standard for Occupational and Educational Personal Eye and Face Protection Devices ANSI Z87.1. (These eye-protection devices are marked “Z87.”)

b.    Where there is a possibility of a hazard from flying particles, the eye protection must meet the High Impact Testing Requirements of Z87.1 (this eye protection is marked “Z87+”).

c.    An EHS industrial hygienist may be consulted to provide guidance in selecting the proper protection.

d.    Safety Glasses

                                         i.    Safety glasses with side shields are required to be worn by individuals while handling or using chemicals. They must meet the basic impact-resistance provisions of ANSI Z87.1.

                                        ii.    Safety glasses are the minimum protection required when handling chemicals. Safety glasses must be supplemented with goggles and/or face shields when there is a greater risk of exposure to chemical splashes or flying particles (e.g., when pouring or mixing chemicals or cryogens).

                                       iii.    Contact lenses may be worn in work areas. However, contact lenses do not provide eye protection. Safety glasses or goggles must be worn by people who use contact lenses when chemicals are being handled.

e.    Cover Goggles

                                         i.    Cover goggles are required for operations where there is a greater risk of exposure to chemicals and to flying particles. Furthermore, they are required for activities producing airborne eye irritants including gases, vapors, fumes, dusts, and mists. Safety glasses provide no protection against eye irritants.

                                        ii.    Cover goggles are available in several varieties including:

1.    Direct-vented. These allow airflow for comfort and to reduce fogging. Generally, direct-vented goggles are inappropriate for liquid chemical use because the vent ports may allow splashed liquids to pass through. Moreover, they provide no protection against airborne eye irritants (gases, vapors, fumes, dusts, and mists).

2.    Indirect-vented. These allow airflow for comfort and to reduce fogging. These are appropriate for liquid chemical use and will protect the eyes from splashes. However they will not guard against irritating gases, vapors, fumes, dusts, and mists.

3.    Nonvented. These have no vents and are required for operations that produce airborne irritating gases, vapors, fumes, dusts, and mists. They also protect against chemical splashes to the eyes.

f.     Face Shields

                                         i.    Face shields protect the entire face and are required for operations that present a high likelihood of exposure to flying particles or splashes from liquid chemicals or cryogenic fluids.

                                        ii.    Face shields must be worn in conjunction with safety glasses or chemical goggles, because face shields can be lifted up during use, exposing the eyes to hazards.

7.    Respirators

a.    Respirators should not be needed in most laboratory and shop settings. However, if engineering, work practices, and administrative controls are not adequate to minimize an airborne chemical hazard, respiratory protection is required.

b.    Use of respirators requires a hazard evaluation conducted by an industrial hygienist. All respirator users must be medically qualified, trained, and fit-tested to wear respiratory protection equipment.

c.    An industrial hygienist must approve procurement of respirators.

d.    Any questions regarding the need for or use of respirators should be directed to an EHS industrial hygienist. Berkeley Lab respirator policy may be found in the ES&H Manual  Respiratory Protection program.

Work Process J. Work Practice Controls

Work practice controls include preplanning work, practicing good housekeeping, maintaining personal hygiene to minimize exposure to hazardous materials, and using common sense. Work practice controls must be used regardless of the type of hazardous material handled.

1.    Work Planning

a.    Pre-plan work: Stage tools, equipment, and materials in advance of the activity to be performed.

b.    Establish designated areas for work involving particularly hazardous substances and engineered nanomaterials. 

c.    Stay upwind or use exhaust ventilation for operations that emit vapors, gases, fumes, dusts, mists, or aerosols.

d.    Limit the amount of hazardous materials procured, used, and stored to the minimum needed for an operation.

e.    Keep drip pans, secondary containment and cleanup materials readily available. 

f.     Be familiar with the use, limitations, and location of emergency equipment such as emergency eyewashes, safety showers, fire alarms, exits, and fire extinguishers.

g.    Keep containers covered when not being used.

h.    Remove jewelry to prevent contact with electrical sources and chemicals and from catching on laboratory or shop equipment.

i.      Confine long hair and loose clothing when working in the laboratory/shop.

2.    Housekeeping

a.    Keep work areas clean and free of obstructions. Clean the work area at the completion of an operation or at the end of the day.

b.    Wipe drips and residues from containers of hazardous materials. Skin contact with residues may cause dermal absorption, chemical burns, skin irritation, and possible accidental ingestion as a result of hand-to-mouth transfer.

c.    Clean surfaces (countertops, bench tops, fume hoods, and floors) of all drips and residues.

d.    Clean spilled chemicals immediately, and dispose of all wastes properly. Spill response is discussed later. Chemical wastes must be disposed of in accordance with the ES&H Manual Waste Management program.

e.    Maintain access to exits, emergency equipment, and other control equipment. Do not use stairways and hallways as storage areas. Store equipment and chemicals properly, and avoid clutter.

3.    Personal Hygiene

  hand wash

a.    After handling chemicals, wash hands with soap and water before leaving the laboratory/shop area and prior to breaks and consumption of food/beverages.

b.    Always remove gloves before touching common use items such as phones, doorknobs, and computers. This will prevent contamination of unprotected individuals.

4.    Food, Beverage, Cosmetics, and Medicine in Technical Areas

a.    Food and beverages (including water, gum, and medicines) may not be consumed or stored in technical areas. Exceptions may be granted in accordance with the procedure described in ES&H Manual Personal Protective Equipment (PPE) program, Appendix A, PPE and Food/Drink Requirements and Responsibilities Table.

b.    Cosmetics, ointments, skin cream, and similar items may not be applied or stored in technical areas.

c.    See Work Process K.1.b, Refrigerators Used for Hazardous Material Storage, for requirements regarding food storage in refrigerators.

d.    Do not use laboratory glassware or utensils to prepare or consume food or beverages.

5.    Use of Glassware

glassware

a.    Never use mouth suction to pipette chemicals or to start a siphon; use mechanical means, a pipette bulb, or an aspirator.

b.    Use adequate hand protection (e.g., proper gloves) when inserting glass tubing into rubber stoppers or corks or when placing rubber tubing on glass hose connections. Tubing should be fire-polished or rounded and lubricated, and hands should be held close together to limit movement of glass should fracture occur. Plastic or metal connectors should be used whenever possible.

c.    Do not attempt glassblowing operations unless proper annealing facilities are available.

d.    Handle vacuum-jacketed glass apparatus with extreme care to prevent implosions. Equipment such as dewar flasks should be taped or shielded. Only glassware designed for vacuum work should be used for that purpose. Consult the ES&H Manual Pressure Safety and Cryogenics program, for the safe use of pressurized and evacuated systems.

e.    Protect hands (i.e., wear tear- and puncture-resistant gloves) when picking up broken glass.

6.    Disposal of Glassware. Dispose of glass in marked cardboard boxes designated for that purpose. Glassware must be free of liquids prior to disposal. Consult Section 2.2, Solid Medical/Biohazardous Waste Disposal, of the Medical and Biohazardous Waste Generator’s Guide (PUB-3095) for guidance on disposing of glassware that has been used for biological work or that may be contaminated with a biohazardous material.

disposal

 

7.    Administrative Controls. Administrative controls include written procedures, employee training, establishing designated or restricted areas, chemical procurement procedures, and preventive maintenance. The development and use of written safety authorizations are discussed in the ES&H Manual Safe Work Authorizations program. Training is discussed in Work Process W, Training, and Work Process X, Hazard Information. The establishment and use of designated areas are discussed in Work Process M, Specific Controls and Procedures — Particularly Hazardous Substances: Carcinogens, Reproductive Toxins, and Acute Toxins.  

Work Process K. Chemical Storage

This section provides requirements and recommendations for storing hazardous materials. Refer to Work Process E, Chemical Hazard Descriptions, and Work Process F, Chemical Hazard Assessments, to determine whether a chemical, material, product, or mixture is hazardous. Refer to the ES&H Manual Waste Management program for hazardous waste storage requirements.

1.    Hazardous Materials Storage Requirements. The criteria listed in this section are requirements that must be followed by Berkeley Lab staff.

a.    General Requirements, Storage Cabinets, and Shelves

  chem storage

                                      i.    Segregate incompatible chemicals (e.g., store oxidizing acids and flammable solvents in separate locations). This is to prevent inadvertent mixing of incompatible chemicals, which can produce harmful gases/vapors, heat, fire, and explosions. Consult specific controls and procedures described in Work Process L through Work Process T of this program for additional requirements and details tailored for various categories of hazardous materials. The chemical incompatibility matrices and tables presented later in this section provide recommended (optional) guidelines for segregating incompatible chemicals.

                                     ii.    Store hazardous materials away from heat and direct sunlight. Heat and sunlight may affect and degrade chemicals and deteriorate storage containers and labels.

                                    iii.    Do not store hazardous materials (except cleaners) under sinks. 

                                   iv.    Ensure caps and lids are securely tightened on containers. This prevents leaks and evaporation of contents.

                                    v.    Use approved flammable storage lockers or flammable storage containers to store flammable and combustible liquids exceeding 10 gallons in one room. Flammable and combustible liquids kept in squeeze bottles and other secondary containers may be kept on counter and bench tops provided they do not exceed the 10-gallon limit and are kept in secondary containment. Note: Storage of non-flammable solvents such as chloroform and methylene chloride are permitted in flammable storage lockers provided that (1) they are chemically compatible with the other stored chemicals and (2) storage of non-flammables does not displace flammable and combustible chemicals from the storage cabinet. See Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids, for additional requirements and details on storage.

                                   vi.    Store inorganic acids in corrosive or acid storage cabinets. See Control Procedures for Acids and Bases for additional requirements. Their interiors and hardware (door hinges and shelf brackets) are corrosion resistant. Corrosive storage cabinets can be located under fume hoods or exist as stand-alone units. Flammable storage cabinets are not corrosion resistant and shall not be used for inorganic acid storage.

                                  vii.    Install Plexiglas lips or use equivalent means to prevent materials from falling off open storage shelves.

b.    Refrigerators Used for Hazardous Material Storage

  fridge

                                      i.    Refrigerators used for storing flammable and combustible liquids shall be designed for that purpose. Do not use ordinary domestic units. See Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids, for additional requirements.

                                     ii.    Do not store food in refrigerators located in technical areas.

                                    iii.    Label refrigerators used for storing chemicals, samples, or media as follows: “Caution Do Not Store Food or Beverages in This Refrigerator.” Labels may be fabricated by users provided they are legible and securely affixed to the refrigerator.

                                   iv.    Refrigerators used for food and beverages outside of technical areas require no posting.

c.    Squeeze Bottles and Wash Bottles. Hazardous materials are often transferred to squeeze bottles and other plastic containers such as Nalgene® bottles. These are made of plastics such as high-density polyethylene, low-density polyethylene, and polypropylene and may exhibit varying degrees of resistance to chemicals. Moreover, they may deteriorate over time, especially when exposed to sunlight or UV sources. Utilize resources such as user knowledge or chemical-resistance data such as that provided by the Nalgene® Web site  to determine and select the proper material.

  squeeze bottles

d.    Secondary Containment

                                      i.    Store liquid hazardous materials (including squeeze and wash bottles) in secondary containment. This is to minimize the impact and spread of spills resulting from broken/leaking containers. Secondary containment capacity must be 110% of the largest container or 10% of the aggregate volume of all containers, whichever is larger.

                                     ii.    Secondary containment is available in different materials that provide varying resistance to various chemicals. Use resources such as user knowledge or the information provided below to select the proper material.

                                   iii.    Photo Trays

1.    Generally, these provide good resistance to aqueous solutions and some organic solvents. But they may not be a good choice for halogenated solvents.

2.    Photo trays are available through several commercial sources, including VWR Scientific. An additional source of spill containment trays is Scientific Plastics. This company provides trays in several depths, with width and length in 1-inch increments. These trays have been used at Berkeley Lab to contain entire shelves in storage cabinets.

                                   iv.    Polypropylene and High-Density Polyethylene Trays

1.    These may be affected by some aromatic and halogenated hydrocarbons.

2.    The Nalgene® Web site has a chemical-resistance database for these materials.

                                    v.    Stainless Steel and Pyrex Trays. Stainless steel and Pyrex trays are resistant to a broader spectrum of chemicals. However, they are more costly than plastic trays and aren’t available in as many different sizes and configurations.

                                   vi.    Larger-Capacity Containers. Containers such as Palletote® boxes are acceptable for larger volumes of liquids provided they are resistant to the chemicals stored in them. Palletote® boxes are constructed of high-density polyethylene.

2.    Hazardous Material Storage Recommendations. The information, guidelines, chemical incompatibility matrices, and tables presented below are recommended good practices. These are optional guidelines.

a.    General Recommendations

                                      i.    Shelves and racks should have enough clearance to accommodate the largest container with room for it to be removed and returned without tipping. Tipping containers when returning them to shelves, cabinets, and refrigerators may cause the contents to drip or leak.

                                     ii.    Limit hazardous materials kept in fume hoods to the amount that is in use or needed for an activity.

                                    iii.    Avoid stockpiling chemicals. 

                                   iv.    Purchase only what is needed. If possible, borrow chemicals from a colleague or contact the Chemical Management System Coordinator to assist you in finding a source of the chemical at Berkeley Lab.

                                    v.    Conduct periodic cleanouts to minimize accumulating unwanted chemicals.

b.    Chemical Incompatibility Matrices and Tables. Chemical incompatibility data are presented in Tables K-1 and K-2 below. These are recommended guidelines that may be used in combination with container labels, MSDSs, and user knowledge for storing and segregating chemicals. An EHS industrial hygienist may also be consulted.

Table K-1. Incompatibilities by Hazard Class

 

Acids, inorganic

Acids, oxidizing

Acids, organic

Alkalis (bases)

Oxidizers

Poisons, inorganic

Poisons, organic

Water- reactives

Organic solvents

Acids, inorganic

 

 

X

X

 

X

X

X

X

Acids, oxidizing

 

 

X

X

 

X

X

X

X

Acids, organic

X

X

 

X

X

X

X

X

 

Alkalis (bases)

X

X

X

 

 

 

X

X

X

Oxidizers

 

 

X

 

 

 

X

X

X

Poisons, inorganic

X

X

X

 

 

 

X

X

X

Poisons, organic

X

X

X

X

X

X

 

 

 

Water-reactives

X

X

X

X

X

X

 

 

 

Organic solvents

X

X

 

X

X

X

 

 

 


Table K-2. Chemical Incompatibility Table

Chemical

Keep out of Contact With

Acetic acid

Chromic acid, nitric acid, perchloric acid, peroxides, permanganates and other oxidizers

Acetone

Concentrated nitric and sulfuric acid mixtures, and strong bases

Acetylene

Chlorine, bromine, copper, fluorine, silver, mercury

Alkali metals

Water, carbon tetrachloride, or other chlorinated hydrocarbons, carbon dioxide, halogens

Ammonia, anhydrous

Mercury, chlorine, calcium hypochlorite, iodine, bromine, hydrofluoric acid

Ammonium nitrate

Acids, metal powders, flammable liquids, chlorates, nitrites, sulfur, finely divided organic or combustible materials

Aniline

Nitric acid, hydrogen peroxide

Arsenic materials

Any reducing agent

Azides

Acids

Bromine

Same as chlorine

Calcium oxide

Water

Carbon (activated)

Calcium hypochlorite, all oxidizing agents

Carbon tetrachloride

Sodium

Chlorates

Ammonium salts, acids, metal powders, sulfur, finely divided organic or combustible materials

Chromic acid and chromium trioxide

Acetic acid, naphthalene, camphor, glycerol, glycerin, turpentine, alcohol, flammable liquids in general

Chlorine

Ammonia, acetylene, butadiene, butane, methane, propane (or other petroleum gases), hydrogen, sodium carbide, turpentine, benzene, finely divided metals

Chlorine dioxide

Ammonia, methane, phosphine, hydrogen sulfide

Copper

Acetylene, hydrogen peroxide

Cumene hydroperoxide

Acids, organic or inorganic

Cyanides

Acids

Flammable liquids

Ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens

Hydrocarbons

Fluorine, chlorine, bromine, chromic acid, sodium peroxide

Hydrocyanic acid

Acids

Hydrofluoric acid

Ammonia, aqueous or anhydrous, bases and silica

Hydrogen peroxide

Copper, chromium, iron, most metals or their salts, alcohols, acetone, organic materials, aniline, nitromethane, flammable liquids

Hydrogen sulfide

Fuming nitric acid, other acids, oxidizing gases, acetylene, ammonia (aqueous or anhydrous), hydrogen

Hypochlorites

Acids, activated carbon

Iodine

Acetylene, ammonia (aqueous or anhydrous), hydrogen

Mercury

Acetylene, fulminic acid, ammonia

Nitrates

Sulfuric acid

Nitric acid (concentrated)

Acetic acid, aniline, chromic acid, hydrocyanic acid, hydrogen sulfide, flammable liquids, flammable gases, copper, brass, any heavy metals

Nitrites

Acids

Nitroparaffins

Inorganic bases, amines

Oxalic acid

Silver, mercury

Oxygen

Oils, grease, hydrogen; flammable liquids, solids, or gases

Perchloric acid

Acetic anhydride, bismuth and its alloys, alcohol, paper, wood, grease, and oils

Peroxides, organic

Acids (organic or mineral); avoid friction, store cold

Phosphorus (white)

Air, oxygen, alkalis, reducing agents

Potassium

Carbon tetrachloride, carbon dioxide, water

Potassium chlorate and perchlorate

Sulfuric and other acids, alkali metals, magnesium, calcium.

Potassium permanganate

Glycerin, ethylene glycol, benzaldehyde, sulfuric acid

Selenides

Reducing agents

Silver

Acetylene, oxalic acid, tartaric acid, ammonium compounds, fulminic acid

Sodium

Carbon tetrachloride, carbon dioxide, water

Sodium nitrite

Ammonium nitrate and other ammonium salts

Sodium peroxide

Ethyl or methyl alcohol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural

Sulfides

Acids

Sulfuric acid

Potassium chlorate, potassium perchlorate, potassium permanganate (or compounds with similar light metals, such as sodium, lithium, etc.)

Tellurides

Reducing agents

(From Manufacturing Chemists' Association, Guide for Safety in the Chemical Laboratory, pp. 215–217, Van Nostrand)

Work Process L. Specific Controls and Procedures — Acids and Bases

1.    Acids and bases are corrosive and will destroy body tissue. The extent of injury depends on factors such as the type and concentration of the chemical, the route of exposure, the type of tissue contacted, and the speed used in applying emergency measures. Acids, especially in concentrated form, are most likely to cause immediate pain upon contact with tissues. High concentrations of hydrofluoric acid will cause immediate pain and tissue destruction. These effects may be delayed by several hours with weaker concentrations. Fluoride ion from hydrofluoric acid also penetrates the deep tissue layers and can cause bone damage. Skin contact with strong bases usually goes unnoticed, since pain does not occur immediately.

2.    The eyes are especially susceptible to acids and bases and must be immediately flushed with water for at least 15 minutes if exposure occurs. Inhaling acid fumes and airborne dust and mist from bases irritates the nose, throat, and lungs. Pulmonary edema, a severe irritation of the lungs resulting in fluid production that prevents the transfer of oxygen to the bloodstream, can also occur from intense extreme airborne exposures. Secondary toxic effects may occur if the material is absorbed from the lungs into the bloodstream. The extent of these effects depends on the concentration in air and the duration of exposure. Ingestion causes severe burns of the mucous membranes of the mouth, throat, esophagus, and stomach.

3.    Dilution of acids and bases is exothermic. This is particularly true for sulfuric acid and potassium hydroxide. Concentrated solutions of inorganic acids and bases are not in themselves flammable. Combustion can occur, however, when an oxidizing acid is mixed with other chemicals or with combustible materials. Acids also react with many metals, resulting in the liberation of hydrogen, a highly flammable gas. Bases such as sodium hydroxide will liberate hydrogen gas upon reaction with aluminum, magnesium, tin, and zinc metal. Some acids are strong oxidizing agents and can react destructively and violently when they come in contact with organic or other oxidizable materials. Perchloric acid may form explosive perchlorate crystals, which are shock-sensitive and can detonate. Acids can form toxic reaction products when combined with cyanide or sulfide salts. The corresponding products are hydrogen cyanide and hydrogen sulfide gas.

4.    Control Measures

a.    Work leads are responsible for identifying acids and bases used in the work area. Review sources such as MSDSs for specific compounds. 

b.    An assessment of the hazards and controls in place is necessary to limit employee exposures to these agents. Contact an EHS industrial hygienist to provide assistance. This is especially important for hydrofluoric and perchloric acids, aqua regia, and piranha etch.

c.    Some operations involving acids and bases may require an AHD. This is determined by the using division in accordance with the provisions in the ES&H Manual Safe Work Authorizations program.  

5.    Training and Information

a.    Employees who either handle or who may be exposed to the hazards of acids and bases are required to complete Chemical Hygiene and Safety Training (EHS0348; or EHS0345 for Facilities personnel or 352 for summer students). 

b.    All employees in the work area should be trained in the specific hazards and controls of these materials. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The area entrance must be posted with a Caution Placard that depicts hazards and conveys hazard and emergency contact information.

6.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives if possible.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator for assistance in locating a source of the chemical at Berkeley Lab.

c.    Conduct periodic cleanouts to prevent accumulation of unnecessary chemicals.

d.    Procure and use the minimum amount of material required for the operation, or

e.    Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals. 

f.     Enter these materials into the Chemical Management System (CMS).

7.    Ventilation

a.    A fume hood or other appropriate exhaust ventilation must be used when handling acids and bases in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes procedures such as transfer operations, preparation of mixtures, blending, sonication, spraying, and heating. 

b.    Operations involving heating or evaporating perchloric acid must be evaluated by an EHS industrial hygienist to determine whether special controls (such as using an acid fume hood with wash-down systems to prevent the accumulation of explosive perchlorate crystals) are needed. 

8.    Work Practices

a.    Transfer containers of acid and base solutions in bottle carriers.

b.    Do not pour water into acid. Slowly add the acid to the water and stir.

c.    Never empty carboys or drums of chemicals by means of air pressure. Use a tilting rack, a safety siphon, or a liquid pump.

d.    Use a mechanical aid or a pipette bulb for pipetting.

e.    Open bottles or carboys slowly and carefully, and wear protective equipment to guard hands, face, and body from splashes, vapors, gases, and fumes.

f.     Wipe drips from containers and bench tops. Be especially careful to wipe up visible residues of sodium hydroxide and potassium hydroxide from all surfaces. Skin contact with dry residue will result in burns.

g.    Do not eat; drink; smoke; chew gum; apply cosmetics; or store food, beverages, and tobacco products in work areas where acids and bases are being used.

9.    Personal Protective Equipment (PPE)

a.    Skin and eye contact must be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

b.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

c.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial-hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

d.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

e.    The primary concerns with acids and bases are chemical burns. However, since many chemicals are skin-absorbers (i.e., agents that readily pass through the skin), it is important to select gloves that are chemically resistant to the material. Consult Work Process I, Personal Protective Equipment, which contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

f.     Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may degrade the gloves, allow the chemical to permeate the gloves and ultimately expose the wearer to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

g.    Note Regarding Chemically Resistant Gloves for Hydrofluoric Acid: Although Best 8005 N-Dex Plus nitrile gloves are provided with the HF Exposure Kit (discussed below) and are suitable for applying calcium gluconate gel once the acid has been flushed from the skin, these may not be the appropriate gloves for handling hydrofluoric acid during laboratory operations, as they offer limited chemical resistance under heavy exposure conditions. In selecting the appropriate gloves for hydrofluoric acid, as with all chemicals, the following considerations must be made: the gloves’ chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Consult Work Process I.5, Gloves, for further information and glove selection. The Web link to the ChemRest Guide to Chemical Resistant Best Gloves provided in that section lists a number of alternatives to the Best 8005 N-Dex Plus nitrile gloves.

10. Storage

a.    start flagConsult Work Process K, Chemical Storage, for hazardous material storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below.

b.    Segregate acids from bases.

c.    Segregate acids from reactive metals such as sodium, potassium, and magnesium.

d.    Segregate oxidizing acids from organic acids and flammable and combustible materials.

e.    Segregate acids from chemicals that could generate toxic or flammable gases upon contact, such as sodium cyanide, iron sulfide, and calcium carbide.

f.     Store inorganic acids in corrosive- or acid-storage cabinets. Their interiors and hardware (door hinges and shelf brackets) are corrosion resistant. Corrosive-storage cabinets can be located under fume hoods or exist as stand-alone units. Flammable-storage cabinets are not corrosion resistant and must not be used for acid storage.

g.    Store acids and bases in sealed, air-impermeable containers with tight-fitting caps, as opposed to loose-fitting lids or glass stoppers. An exception to this is mixtures that may produce gases that can pressurize the container. These include piranha etch and aqua regia. Piranha etch is a mixture of 98% sulfuric acid and 30% hydrogen peroxide in ratios ranging from 2-4:1. It produces gaseous oxygen. Aqua regia is a 1:3 mixture of concentrated nitric and hydrochloric acids. It produces nitrogen dioxide, chlorine, and nitrosyl chloride gases. Either mix fresh batches and use on the same day, or fit containers with vented caps to prevent overpressurization.

h.    Keep piranha etch and aqua regia in fume hoods at all times. Note: Normally hazardous materials kept in fume hoods should be limited to those that are in use or that are needed for an activity. But because piranha etch and aqua regia may off-gas, these should be kept in a fume hood.

i.      Do not store aqueous sodium and potassium hydroxide solutions in aluminum drip trays. These will corrode aluminum and compromise its integrity.

j.     Store nitric acid in its own secondary containment trays. Nitric acid can combine with other acids to form nitrogen oxides and nitrosyl halide gases.

k.    Store combustible organic carboxylic acids such as acetic acid in a flammable storage locker. end flag

11. Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spill and personal exposure to chemicals.

b.    In addition to these requirements, the following applies to acid and base spills:

                                          i.    Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills. Keep an adequate number of appropriate spill kits to meet anticipated needs.

                                         ii.    Do not clean up or neutralize acid spills with bases (including soda ash, sodium carbonate). In addition, do not neutralize base spills with acids. A potential aggressive and exothermic reaction may ensue. Gaseous carbon dioxide generated from the neutralization reaction can cause splattering. 

                                        iii.    Use commercially available acid and base spill cleanup kits that contain “neutralizing agents” and acid/base (pH) indicators. These neutralize spills at a controlled reaction rate, which eliminates splattering and excessive heat generation. The pH indicator provides a visible color change to indicate complete neutralization of the spill. These are available through VWR Scientific.

                                       iv.    It is important to have a sufficient quantity of neutralizer to handle anticipated needs. For example, a J.T. Baker spill kit contains 3.2 kg of neutralizing agent. This is sufficient to neutralize the following volumes of the indicated acids:

Acid and Concentration

Volume (L) Acid Neutralized by 3.2 kg of JT Baker Neutrasorb®

Hydrobromic acid (38%)

2.6

Hydrochloric (38%)

1.9

Hydroiodic acid (51%)

6.3

Nitric acid (71%)

1.5

Perchloric acid (72%)

2.0

Phosphoric (87%)

0.5

Sulfuric acid (98%)

0.7

Sulfurous acid (9%)

11.5

The J.T. Baker Neutracit® caustic spill cleanup kit has 1.2 kg of neutralizing agent, which has the following neutralizing capacities:


Base and Concentration

Volume (L) Base Neutralized by 1.2 kg of JT Baker Neutracit®

Ammonium hydroxide (28%)

0.75

Potassium hydroxide (45%)

0.66

Sodium hydroxide (50%)

0.47

(NOTE: These products can be bought with larger quantities of neutralizing agents.)

c.    Ensure that you read and understand how to use spill cleanup and neutralizing agents before a spill occurs.

d.    Add neutralizing agents slowly and deliberately. Understand that a chemical reaction will occur that involves some heat generation and the evolution of gas (normally carbon dioxide). 

e.    Note Regarding Spill Kits for Hydrofluoric Acid: Hydrofluoric acid cannot be cleaned up with normal acid spill kits. Do not use silica-containing agents, especially diatomaceous earth (kitty litter) and sand, to absorb hydrofluoric acid, because they can react with HF to form toxic silicon tetrafluoride gas. Use spill kits such as HF Acid Eater (NPS Corp.) or HF Spill Tamer (J.T. Baker/Mallinckrodt). HF is a weak acid and does not completely dissociate. Therefore, sufficient time must be allowed for the neutralizing agent to neutralize the acid. 

f.     An emergency eyewash and safety shower must be located in all areas where acids or bases are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment.

g.    Note Regarding Contact with Hydrofluoric Acid and First Aid: Any suspected skin contact with hydrofluoric acid or gas should be treated with flushing as described above, except that flushing should be done for a 5-minute instead of a 15-minute period. Flushing may remove surface hydrofluoric acid, but it does not affect the fluoride ion, which may have penetrated to the deep tissue layers. All work areas where hydrofluoric acid is used must have at least one HF exposure kit. These consist of calcium gluconate gel, Best 8005 N-Dex Plus nitrile gloves for applying the gel, and instructions on what to do in case of exposure. (See Note Regarding Chemically Resistant Gloves for Hydrofluoric Acid, above, regarding the limitations of Best 8005 N-Dex Plus nitrile gloves for normal laboratory operations). Hydrofluoric acid exposure kits are available through Health Services (ext. 6266). If exposed, flush the affected area for 5 minutes, don the Best 8005 N-Dex Plus (8-mil-thick) nitrile gloves, liberally apply the gel to the affected areas (not the eyes), and report to Health Services immediately.

Work Process M. Specific Controls and Procedures — Particularly Hazardous Substances: Carcinogens, Reproductive Toxins, and Acute Toxins

OSHA has established a category of chemicals known as particularly hazardous substances for which special precautions may be required. Particularly hazardous substances include select carcinogens, reproductive toxins, and substances with a high degree of acute toxicity. The Web resources listed below, container labels and MSDSs should be reviewed to identify these hazards. The Chemical Management System (CMS) can also be used to identify these substances in a work area.

1.    Carcinogens. Carcinogens are agents that cause neoplasms (tumors) in humans and/or animals. Carcinogenic agents may be organic chemicals, inorganic chemicals, or hormones. Some carcinogens react directly with a cell’s genetic information (the DNA), causing changes (mutations) that are incorporated into subsequent generations of that cell. Select carcinogens are agents that are strongly implicated as sources of cancer in humans. Lists of select carcinogens and other resources are available in Appendix C of this program.

2.    Reproductive Toxins. Reproductive toxins are agents that affect reproductive capabilities, including chromosomal damage (mutations), and produce effects on developing fetuses (teratogenesis). Reproductive toxins can affect both men and women. Examples of adverse reproductive health effects include birth defects, spontaneous abortion, fetal developmental damage, and infertility. It is important to note that the first trimester of pregnancy is the period of most concern to the developing fetus because this is when the organs and the limbs are being formed. During this period, many women may not yet be aware that they are pregnant. For this reason, it is important that the use of reproductive toxins have been identified and that control measures are in place to protect a woman and her fetus from harmful exposure levels. Women who are (or are trying to become) pregnant may consult with Health Services before the start of any laboratory or shop activity involving reproductive toxins. A list of reproductive toxins is provided in the Appendices.

3.    Acutely Toxic Substances. Substances of high acute toxicity include materials that may be fatal or cause damage to target organs from a single exposure or from exposures of short duration. They also include materials capable of causing intense irritation that can result in pulmonary edema (fluid and swelling in the lungs), chemical asphyxia, and systemic (bodywide) poisoning. It is not practical to provide a list of all substances of high acute toxicity in this document. The MSDS should be consulted to determine the toxicity of all substances. An EHS industrial hygienist may also be consulted for additional guidance.

4.    Control Measures

a.    Work leads are responsible for identifying particularly hazardous substances used in the work area. Review sources such as MSDSs for specific compounds. 

b.    An assessment of the hazards and controls in place is necessary to limit employee exposures to these agents. Contact an EHS industrial hygienist to provide assistance.

c.    Some operations involving these materials may require an AHD. This is determined by the using division in accordance with the provisions in the ES&H Manual Safe Work Authorizations program.

d.    OSHA requires that the following four categories of controls be considered for operations and activities involving particularly hazardous substances:

                                          i.    Establish posted designated areas. A designated area may be a room, a section of a room, a bench top or a containment device (such as a lab hood). Requirements may be found in the section titled Designated Areas. NOTE: When handling substances (in nonlaboratory settings) that are regulated by OSHA substance-specific standards (such as asbestos), “regulated areas” will be established in accordance with the applicable OSHA standard.

                                         ii.    Use containment devices (such as fume hoods, gas cabinets, glove boxes or the equivalent).

                                        iii.    Implement contaminated-waste removal procedures. NOTE: Compliance with Berkeley Lab waste-handling policy and procedures as addressed in the ES&H Manual Waste Management program satisfies this requirement.

                                       iv.    Establish decontamination procedures. These are necessary to prevent the spread of contamination to other areas. Decontamination procedures include practicing good housekeeping by wiping down work surfaces at the end of the day and cleaning up drips, residues, and spills. Cleanup materials used (such as absorbents and cloths) must be disposed of as hazardous waste. NOTE: Wipe sampling, as described in Work Process CC, Exposure Assessment, Monitoring, and Medical Consultation, may be required to confirm the effectiveness of decontamination procedures.

5.    Training and Information

a.    Employees who either handle or who may be exposed to particularly hazardous substances must complete Chemical Hygiene and Safety Training (EHS0348; or 345 for Facilities personnel or 352 for summer students).

b.    All employees in the work area must be trained in the specific hazards and controls of the materials being handled. Furthermore, employees working in designated areas are to be informed of the specific hazards and controls of the materials used. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The area entrance/designated and regulated areas must be posted with a Caution Placard depicting hazards and emergency contact information.

6.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives if possible.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator to assist you in finding a source of the chemical at Berkeley Lab.

c.    Conduct periodic cleanouts to prevent accumulating unneeded chemicals.

d.    Procure and use the minimum amount of material required for the operation, or

e.    Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.

f.     Enter these materials into the Chemical Management System (CMS).

7.    Ventilation

Use local exhaust ventilation such as a fume hood or glove box when handling particularly hazardous substances in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes operations such as transfer operations, preparation of mixtures, blending, sonification, spraying, heating, and distilling. See Work Process H, Selection and Use of Engineering Controls, for more information.

8.    Work Practices

a.    Transfer containers in bottle carriers.

b.    Do not eat, drink, smoke, chew gum or tobacco, store food, or apply cosmetics in work or storage areas.

c.    Use a mechanical aid or a pipette bulb for pipetting.

d.    Open bottles or carboys slowly and carefully and wear protective equipment to guard hands, face, and body from splashes and vapors/gases.

e.    Wipe drips/residues from containers and work surfaces. To facilitate decontamination, use stainless steel or plastic trays, absorbent paper with a moisture-proof lining, or other impervious material.

f.     Upon completion of the operation, decontaminate or discard the protective covering material as hazardous waste.

g.    Wash hands before leaving the work area and prior to consuming food/beverages.

h.    Do not eat; drink; smoke; chew gum; apply cosmetics; or store food, beverages, and tobacco products in work areas where particularly hazardous substances are being used.

9.    Personal Protective Equipment (PPE). Skin and eye contact must be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

a.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

b.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

c.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

d.    Because many chemicals are skin-absorbers (i.e., agents that readily pass through the skin) it is important to select gloves that are chemically resistant to the material. Consult the PPE section, which contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

e.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately, personal exposure to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

10. Storage

a.    start flagConsult Work Process K, Chemical Storage, for hazardous-material storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below.

b.    Follow the storage guidelines in Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids, if the material is either flammable or combustible. end flag

11. Emergency Procedures. Refer to Work Process V, Emergency Procedures and Equipment, for Berkeley Lab policy and response procedures for chemical spills and personal exposure to chemicals.

 Work Process N. Specific Controls and Procedures — Flammables and Combustible Liquids

1.    General Information

a.    Flammable and combustible chemicals include liquids such as organic solvents, oils, greases, tars, oil-base paints, and lacquers, as well as flammable gases. Flammable gases are discussed in ES&H Manual programs, Pressure Safety and Cryogenics and Gas Safety. The emphasis of this section is on flammable and combustible liquids.

b.    Flammable and combustible liquids are defined by their flash points. The flash point of a liquid is the minimum temperature at which it gives off sufficient vapor to form an ignitable mixture with the air near its surface or within its containment vessel. A liquid’s flash point is a function of its vapor pressure and boiling point. Generally, the higher the vapor pressure and the lower the boiling point of a liquid, the lower its flash point will be. The lower the flash point, the greater the fire and explosion hazard

c.    Flammable and combustible liquids are classified by the National Fire Protection Association (NFPA) based on their flash points:

2.    Flammable Liquids (Class I)

a.    Liquids with flash points below 100°F (37.8°C) and vapor pressures not exceeding 40 pounds per square inch (absolute) at 100°F (37.8°C). Flammable Class I liquids are subdivided as follows:

                                          i.    Class IA: Liquids having flash points below 73°F (22.8°C) and boiling points below 100°F (37.8°C). Flammable aerosols (spray cans) are included in Class IA.

                                         ii.    Class IB: Liquids having flash points below 73°F (22.8°C) and having boiling points at or above 100°F (37.8°C).

                                        iii.    Class IC: Liquids having flash points at or above 73°F (22.8°C) and below 100°F (37.8°C). The boiling point is not considered.

3.    Combustible Liquids (Classes II and III)

a.    Liquids having flash points at or above 100°F (37.8°C). Combustible liquids in Classes II and III are subdivided as follows:

                                          i.    Class II: Liquids having flash points at or above 100°F (37.8°C) and below 140°F (60.0°C).

                                         ii.    Class IIIA: Liquids having flash points at or above 140°F (60.0°C) and below 200°F (93.4°C).

                                        iii.    Class IIIB: Liquids having flash points at or above 200°F (93.4°C).

4.    Control Measures

a.    Work leads must identify flammable and combustible liquids used in the work area. Review sources such as MSDSs for specific compounds. 

b.    An assessment of the hazards and controls in place is necessary to limit employee exposures to these agents. Contact an EHS industrial hygienist to provide assistance.

c.    Some operations involving flammable and combustible liquids may require an Activity Hazard Document (AHD). This is determined by the using division in accordance with the provisions in the ES&H Manual Safe Work Authorizations program.

5.    Training and Information

a.    Employees who either handle or who may be exposed to flammable and combustible liquids are required to complete Chemical Hygiene and Safety Training (EHS0348; or EHS0345 for Facilities personnel or 352 for summer student.

b.    All employees in the work area must be trained in the specific hazards and controls of the materials being handled. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The entrance to the work area should be posted with a Caution Placard depicting hazards and emergency contact information.

6.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives (e.g., materials with higher flash points and higher boiling points) if possible.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator to assist you in finding a source of the chemical at Berkeley Lab.

c.    Conduct periodic cleanouts to prevent accumulating unneeded chemicals.

d.    Procure and use the minimum amount of material required for the operation, or

e.    Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.

f.     Enter these materials into the Chemical Management System (CMS).

7.    Ventilation. A fume hood or other appropriate exhaust ventilation system should be used when handling flammable and combustible liquids in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes procedures such as transfer operations, preparation of mixtures, blending, sonification, spraying, heating, and distilling.

8.    Work Practices

a.    Control all ignition sources when handling flammable and combustible liquids.

b.    Electrically bond and ground containers when transferring Class I flammable liquids and other flammable and combustible liquids at temperatures above their flash points.

c.    Storing and consumption of food is permitted in designated areas only. See Work Practice Controls for additional information.

d.    Use a mechanical aid or a pipette bulb for pipetting.

e.    Open bottles or carboys slowly and carefully and wear protective equipment to guard hands, face, and body from splashes and vapors/gases.

f.     Wipe drips/residues from containers and work surfaces.

g.    Wash hands before leaving the work area and prior to consuming food/beverages.

9.    Personal Protective Equipment (PPE). Skin and eye contact must be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

a.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings) and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

b.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial-hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

c.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

d.    Because many chemicals are skin-absorbers (i.e., agents that readily pass through the skin) it is important to select gloves that are chemically resistant to the material. Consult the PPE section. This contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

e.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

10. Storage

a.    start flag Consult Work Process K, Chemical Storage, for hazardous-materials storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below. end flag

b.    Store flammable and combustible liquids away from ignition sources (heat, sparks, open flames).

c.    Segregate flammable and combustible liquids from oxidizing acids and oxidizers.

d.    Flammable-Storage Lockers and Refrigerators

                                          i.    Store flammable and combustible liquids totaling more than 10 gallons in one room or laboratory in an approved flammable-storage cabinet. Note: Storage of non-flammable solvents such as chloroform and methylene chloride are permitted in flammable storage lockers provided that (1) they are chemically compatible with the other stored chemicals and (2) storage of non-flammables does not displace flammable and combustible chemicals from the storage cabinet. Flammable-storage cabinets are designed to protect their contents from fires in the work area. They can be located under fume hoods or exist as stand-alone units. Approved flammable-storage cabinets are constructed of steel and are equipped with self-closing doors with a three-point latch arrangement. Flammable-storage cabinets installed as part of laboratory construction and renovation projects must be connected to the building’s supply and exhaust ventilation system. The top bung is connected to an outside source of supply air and the lower bung is connected to the exhaust system. This controls vapors and odors and prevents corrosion to the interior.

                                         ii.    No more than 120 gallons of Class I, Class II, and Class IIIA liquids, combined, may be stored in a flammable-storage cabinet. Of this total, no more than 60 gallons may be Class I and Class II liquids, combined, and not more than three such cabinets may be in a single fire-control area. (i.e., an area that is separated from other rooms/areas by fire walls).

                                        iii.    Do not store Class I liquids in any basement or pit unless it has an approved ventilation system designed to prevent the accumulation of flammable vapors (refer to OSHA 1910.106[f][2][iii][b]). A basement is a story of a building or structure having one-half or more of its height below ground level. For questions or further guidance, consult the Berkeley Lab Fire Marshal.

                                       iv.    Ordinary domestic refrigerators and freezers contain electrical components (light bulbs, switches, contacts, and motors) that are potential ignition sources that may initiate a fire or an explosion if flammable vapors are present. Therefore, refrigerators and freezers used for storing flammable liquids must be designed, constructed, approved, and labeled for that purpose. NOTE: This applies to aqueous ethanol solutions greater than or equal to 15%. Domestic refrigerator and freezers as well as units that have been modified to remove spark sources are not acceptable alternatives. Contact Procurement & Property Management for guidance on purchasing refrigerators and freezers.

e.    Flammable and Combustible Storage Cans and Other Containers. Flammable and combustible liquids may be stored in various containers. The allowed volume depends on the flammable/combustible class and container material (See Table N-1 below).

Table N-1. Containers for Combustible and Flammable Fluids

 

Flammable Liquid Class

Combustible Liquid Class

Container Type

IA

IB

1C

II

III

Glass

1 pta

1 qt a

1 gal

1 gal

start flag 1 gal end flag

Metal (other than Department of Transportation [DOT] drums)

1 gal

5 gal

5 gal

5 gal

5 gal

Approved safety cansb

2 gal

5 gal

5 gal

5 gal

5 gal

Metal drums (DOT specifications)

60 gal

60 gal

60 gal

60 gal

60 gal

Approved portable tanks

660 gal

660 gal

660 gal

660 gal

660 gal

a Glass containers of no more than 1 gallon capacity may be used for Class IA or IB flammable liquids if such liquid either would be rendered unfit for its intended use by contact with metal or would excessively corrode a metal container so as to create leakage hazard. NOTE: This exemption does not apply to the accumulation of noncorrosive ignitable hazardous waste.

b Underwriter Laboratory or Factory Mutual approved container equipped with a self-closing lid, pressure relief, flame arrester, bonding/grounding tab, and a funnel.

 

f.     Note: Class I liquids are flammable, and Class II liquids are combustible; Class 1A liquids have a flash point (FP) below 73°F, and boiling point (BP) below 100°F; Class 1B — FP below 73°F, and BP at or above 100°F; Class 1C — FP at or above 73°F, but less than 100°F (BP not addressed); Class II — FP at or above 100°F, but below 140°F; Class III — FP at or above 140°F.

g.    Gravity-Dispensing Flammable Liquids. Class IB liquids (e.g., ethanol) may be transferred from containers or tanks by gravity through piping, hoses, and self- or automatic closing valves that have been reviewed and approved by the Laboratory’s Fire Marshal. Such transfer operations must be done with spill control and secondary containment. Moreover, the nozzle and containers must be bonded to each other (i.e., electrically interconnected) to prevent static electricity discharge.

11. Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spill and personal exposure to chemicals

b.    In addition to these requirements, the following applies to flammable and combustible liquid spills:

                                          i.    Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills of flammable or combustible liquids. Keep an adequate number of appropriate spill kits to meet anticipated needs. These are commercially available through VWR Scientific. Typically, products containing diatomaceous earth are used for absorbing organic solvents.

                                         ii.    An emergency eyewash and safety shower should be located in all areas where flammable or combustible liquids are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment.

Work Process O. Specific Controls and Procedures — Laser Dyes and Solvents

1.    General

a.    Dye lasers normally use a lasing medium consisting of a fluorescent organic dye dissolved in an organic solvent. For most dyes, little is known about their toxic properties, except that they are often members of chemical families that contain highly toxic materials. Furthermore, limited testing has indicated that some laser dyes are carcinogenic or mutagenic. Consequently, most dyes should be treated as hazardous chemicals. In many cases, the solvent in which the dye is dissolved plays a major role in the hazards. Most solvents used for dye solutions are flammable and toxic by inhalation and/or skin-absorption.

b.    The following measures were developed to combine the need for a cautious approach to preventing exposures to hazardous chemicals, proper waste management, fire prevention, and practical operating requirements.

2.    Control Measures

a.    Work leads are responsible for identifying laser dyes and solvents used in the work area. Review sources such as MSDSs for specific compounds. 

b.    An assessment of the hazards and controls in place is necessary to limit employee exposures to these agents. Contact an EHS industrial hygienist to provide assistance.

c.    Some operations involving these materials may require an AHD. This is determined by the using division in accordance with the provisions in ES&H Manual Safe Work Authorizations program.

3.    Training and Information

a.    Employees who either handle or who may be exposed to laser dyes and solvents must complete Chemical Hygiene and Safety Training (EHS0348; or 345 for Facilities personnel or 352 for summer students).

b.    All employees in the work area must be trained in the specific hazards and controls of the dyes and solvents being handled. This is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The entrance to the work area must be posted with a Caution Placard depicting hazards and emergency contact information.

4.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives (e.g., nonmutagenic/carcinogenic dyes or less concentrated forms) if possible. Note that some solvents such as dimethyl sulfoxide (DMSO) and methyl alcohol readily penetrate unbroken skin. Hazardous mutagenic or carcinogenic dyes can enter the body through skin-absorption when dissolved in solvents such as these.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator to assist you in finding a source of the chemical at Berkeley Lab.

c.    Conduct periodic cleanouts to prevent accumulating unneeded chemicals.

d.    Procure and use the minimum amount of material required for the operation, or

e.    Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.

f.     Enter these materials into the Chemical Management System (CMS).

5.    Engineering Controls

a.    A fume hood must be used when mixing laser dyes or when handling them in a manner that may generate an airborne hazard (such as fumes, gases, vapors, and mists).

b.    Install spill pans under pumps and reservoirs or, preferably, enclose them. Make sure that knobs and other protuberances extend through the holes in the enclosures.

c.    Leak-test dye pump loops, as appropriate.

6.    Work Practices

a.    Do not eat; drink; smoke; chew gum; apply cosmetics; or store food, beverages, and tobacco products in work areas where laser dyes and solvents are being used.

b.    Use mechanical pipetting aids when handling dye solutions.

c.    Keep containers of solvents and dye solutions closed.

d.    Cap off and/or drain dye lines that are not in use.

e.    Keep the work area clean. Use wet methods for housekeeping in dye work areas. Remove visible stains as much as practical during cleanup. (NOTE: Custodians should not do dye cleanup work.)

f.     Keep flammable solvents in approved storage lockers.

g.    Wash hands after handling laser dyes and solutions.

h.    Personnel who have had skin, eye, or inhalation exposure to dye powders or solutions should contact an EHS industrial hygienist.

i.      Minimize the quantity of pure dye or solutions containing >0.1% of mutagenic/carcinogenic dyes in storage or in use at any time.

j.     Ensure that maintenance and emergency personnel who may come in contact with dyes and solvents are aware of hazards in order for them to take appropriate precautions by posting Caution Placards at entrances to work areas.

k.    Personal Protective Equipment (PPE). Skin and eye contact shall be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

                                          i.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

                                         ii.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial-hygiene hazard evaluation and a medical clearance, followed by a fit test and training by the Industrial Hygiene Group.

                                        iii.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

                                       iv.    Since many chemicals are skin-absorbers (i.e., agents that readily pass through the skin), it is important to select gloves that are chemically resistant to the material. Consult Work Process I, Personal Protective Equipment. This contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

                                        v.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

Table O-1. Glove Selection Table – Glove Material Type1

Solvents

Neoprene

Butyl

PVC

Nitrile

Natural Rubber

Viton

Benzyl alcohol

OK

OK

--

--

--

OK

Dimethyl sulfoxide (DMSO)

--

OK

--

--

--

--

Ethanol (ethyl alcohol)

--

OK

--

--

--

--

Ethylene glycol

OK

--

OK

OK

OK

--

Ethylene glycol phenyl ether (2-phenoxyethanol)

--

OK

--

OK

--

--

Glycerol (glycerin)

OK

OK

OK

OK

OK

OK

Methanol (methyl alcohol)

OK

OK

OK

OK

OK

--

Propylene carbonate

--

OK

--

OK

--

--

Check vendor chemical resistance data BEFORE selecting and buying gloves. DO NOT use unless vendor data demonstrates gloves are acceptable even if they are marked “OK” in this table. Gloves are available from VWR Scientific and other vendors via Berkeley Lab’s Procurement & Property Web page. If you have difficulty obtaining gloves or any other type of PPE, contact an EHS industrial hygienist.

7.    Storage

a.    start flagConsult Work Process K, Chemical Storage, for hazardous-material storage requirements, recommendations, and information on chemical incompatibility. It is recommended that laser dyes be stored separately from solvents. Requirements for storing laser dyes and solvents are provided below.

b.    Follow the storage guidelines in Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids if the material is either flammable or combustible.

c.    Use secondary containment for dye pumps and lines. end flag

8.    Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spills and personal exposure to chemicals.

b.    In addition to these requirements, the following applies to laser dye and solvent spills:

c.    Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills of laser dye and solvents. Keep an adequate number of appropriate spill kits to meet anticipated needs. These are commercially available through VWR Scientific. Typically, products containing diatomaceous earth are used for absorbing organic solvents.

d.    An emergency eyewash and safety shower should be located in all areas where laser dye and solvents are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment.

Work Process P. Specific Controls and Procedures — Peroxide-Forming Compounds

1.    Peroxide Formation. Peroxide formation in common laboratory chemicals is caused by an autoxidation reaction. The reaction can be initiated by exposure to air (oxygen), light (UV radiation), heat, introduction of a contaminant, or the loss of an inhibitor. Some chemicals have inhibitors such as BHT (2,6-di-tert-butyl-4-methyl phenol) hydroquinone and diphenylamine to slow peroxide formation. Most organic peroxide crystals are sensitive to heat, shock, or friction, and their accumulation in laboratory reagents has resulted in numerous explosions. For this reason, it is important to identify and control chemicals that form potentially explosive peroxides.

2.    Peroxide-Forming Compounds. In general, the more volatile the compound, the greater its hazard, since the evaporation of the compound allows the peroxide to concentrate. Peroxide accumulation is a balance between peroxide formation and degradation. Some common compounds that are known to form peroxides are listed in the following table. NOTE: This is not an exhaustive list. Researchers must consult the MSDSs and other sources of information for the chemicals used in their work areas to determine their peroxide-forming potential.

a.    Group A of Table P-1 are chemicals that spontaneously form peroxides on exposure to air without further concentration or evaporation. These materials should be tested or disposed of within three months of opening (testing is discussed later in this section).

b.    Group B of Table P-1 lists chemicals that form peroxides only upon concentration by evaporation or distillation. The materials in this list should be tested or disposed of within one year of opening their containers.

c.    Group C of Table P-1 is a representative list of monomers that form peroxides that may act as a catalyst, resulting in explosive polymerization.


 

Table P-1. Group Peroxide-Forming Chemicals

Group A: Chemicals That Form Explosive Levels of Peroxides without Concentration
(Safe Storage Time after Opening: 3 Months)

Chemical

CAS

Synonyms

State

Reference

Butadiene(1,3)

106-99-0

1,3-Butadiene

G

4

Chloroprene (1,3)

126-99-8

2-Chloro-1,3- butadiene

L

4

Divinyl acetylene

821-08-9

1,5-Hexadien- 3-yne

L

5

Isopropyl ether

108-20-3

 

L

5

Tetrafluoroethylene

116-14-3

 

G

4

Vinyl ether

109-93-3

Divinyl ether

L

5

Vinylidene chloride

75-35-4

1,1- Dichloroethylene

L

5

Group B: Chemicals That Form Explosive Levels of Peroxides on Concentration
(Safe Storage Time after Opening: 12 Months)

Acetal

105-57-7

 

L

5

Acetaldehyde

75-07-0

 

L

4

Benzyl alcohol

100-51-6

 

L

4

2-Butanol

78-92-2

 

l

4

Cyclohexanol 

108-93-0

 

l

4

Cyclohexene 

110-83-8

 

l

5

2-Cyclohexen-1-ol

822-67-3

 

l

4

Cyclopentene

142-29-0

 

l

5

Decahydronaphthalene

91-17-8

 

l

4

Diacetylene

460-12-8

 

g

5

Dicyclopentadiene

77-73-6

 

l

5

Diethylene glycol dimethyl ether

111-96-6

Diglyme

l

5

Group B: Chemicals That Form Explosive Levels of Peroxides on Concentration
(Safe Storage Time after Opening: 12 Months)

Chemical

CAS

Synonyms

State

Reference

Dioxane

123-91-1

1,4-Dioxane

l

5

Ethylene glycol dimethyl ether

110-71-4

Glyme

l

5

Ethyl ether

60-29-7

Diethyl ether

l

5

Furan

128-37-0

 

l

5

4-Heptanol

589-55-9

 

l

4

2-Hexanol

626-93-7

 

l

4

Isopropyl benzene

98-82-8

Cumene

l

5

Methyl acetylene

74-99-7

Propyne

g

5

3-Methyl-1-butanol

123-51-3

Isoamyl alcohol

l

4

Methyl cyclopentane

96-37-7

 

l

5

Methyl isobutyl ketone

108-10-1

Methyl-i-butyl ketone

l

5

4-Methyl-2-pentanol

108-11-2

 

l

4

2-Pentanol

6032-29-7

 

l

4

4-Penten-1-ol

821-09-0

 

l

4

1-Phenylethanol

98-85-1

alpha-Methyl-benzyl alcohol

l

4

2-Phenylethanol

60-12-8

Phenethyl alcohol

l

4

2-Propanol

67-63-0

Isopropanol

l

6, 7

Tetrahydrofuran

109-99-9

 

l

5

Tetrahydronaphthalene

119-64-2

 

l

5

Group C: Chemicals That May Autopolymerize as a Result of Peroxide Accumulation
(Safe Storage Time after Opening: Inhibited Chemicals, 12 Months;

Uninhibited Chemicals, 24 Hours)

Chemical

CAS

Synonyms

State

Reference

Acrylic acid(2)

79-10-7

 

l

5

Acrylonitrile(2)

107-13-1

 

l

5

Butadiene(1,3)

106-99-0

 

g

5

Buten-3-yne

689-97-4

Vinyl acetylene & Butenyne

g

5

Chloroprene(1,3)

126-99-8

2-Chloro-1,3-butadiene

l

5

Chlorotrifluoroethylene

79-38-9

 

g

5

Methyl methracrylate(2)

80-62-6

 

l

5

Styrene

100-42-5

 

l

5

Tetrafluoroethylene

116-14-3

 

g

5

Vinyl acetate

108-05-4

 

l

5

Vinyl chloride

75-01-4

Mono-chloroethylene

g

5

Vinylidene chloride  

75-35-4

1,1-Dichloroethylene

l

5

2-Vinyl pyridine

100-69-6

 

l

5

4-Vinyl pyridine

100-43-6

 

l

5

Table P-1 References:

1.    When stored as a liquid monomer.

2.    Although these form peroxides, no explosions involving these monomers have been reported.

3.    Also stored as a gas in gas cylinders.

4.    Kelly, R.J., Review of Safety Guidelines for Peroxidizable Organic Chemicals, Chemical Health and Safety, September/October, 1996.

5.    National Research Council, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals; National Academy Press; Washington, D.C., 1999. 

6.    Clark, D.E., Peroxides and Peroxide-Forming Compounds, Chemical Health and Safety, September/October, 2001.

7.    This material is peroxidizable but not dangerous unless distilled or concentrated. Testing (see Work Process P.10, Peroxide Testing Method) is required only prior to distillation or concentration.

________________

3.    Control Measures

a.    Work leads must identify peroxide-forming compounds used in the work area. Review sources such as MSDSs for specific compounds. Table P-1; Work Process Y, Container Labeling; MSDSs; and other sources of hazard information (e.g., refer to the EHS Chemical Safety Web page) should be reviewed. Also, use the Chemical Management System to electronically search the chemical inventory for peroxide formers in an area and/or for a specific owner. However, the Chemical Management System is based on the list in Table P-1 and is not an exhaustive method of identifying peroxide-forming compounds.

b.    A hazard assessment of these materials, their use, and the controls in place must be conducted. This should be done in conjunction with an EHS industrial hygienist. Operations involving peroxide-forming chemicals may require an AHD. Consult the ES&H Manual Safe Work Authorizations program to make this determination.

c.    The start flag Peroxide-Forming Chemical Appraisal Process for Divisions end flag is a guide for researchers to evaluate their chemicals.

d.    The start flag Peroxide Forming Chemical Evaluation Sheet end flag provides guidance to determine whether a container is safe to open for testing. Testing is addressed later in this section.

4.    Training and Information

a.    Employees who either handle or who may be exposed to hazardous materials, including peroxide-forming chemicals, must complete Chemical Hygiene and Safety Training (EHS0348; or 345 for Facilities personnel or 352 for summer students).

b.    All employees in the work area require training in the specific hazards and controls of the materials being handled. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag Additional labeling requirements are discussed below.

d.    Entrances to work areas should be posted with a Caution Placard depicting area hazards and emergency contact information.

5.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives (e.g., chemicals that don’t form peroxide crystals).

b.    Otherwise, procure chemicals that have a peroxide inhibitor added (e.g., BHT).

c.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator to assist you in finding a source of the chemical at Berkeley Lab.

d.    Conduct periodic cleanouts to prevent accumulating unneeded chemicals.

e.    Procure and use the minimum amount of material required for the operation, or

f.     Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.

g.    Enter these materials into the Chemical Management System (CMS).

6.    Engineering Controls

a.    A fume hood or other appropriate exhaust ventilation must be used when handling peroxide-forming chemicals in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes procedures such as transfer operations, preparation of mixtures, blending, sonification, spraying, heating, evaporation, and distilling.

b.    Place safety shields in front of reaction vessels, distillation columns, and other apparatuses when fire, explosion, or detonation may occur.

c.    Leave at least 10% bottoms when distilling peroxide-forming chemicals.

7.    Personal Protective Equipment (PPE). Skin and eye contact must be prevented. The following PPE should be worn when handling these materials (Additional information may be found in Work Process I, Personal Protective Equipment:

a.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed- toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

b.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

c.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

d.    Since many chemicals are skin-absorbers (i.e., agents that readily pass through the skin), it is important to select gloves that are chemically resistant to the material. Consult the PPE section. This contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

e.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

8.    Storage

a.    start flagConsult Work Process K, Chemical Storage, for hazardous materials storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below.

b.    Follow the storage guidelines in Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids, if the material is either flammable or combustible.

c.    Store peroxide-forming chemicals in sealed, air-impermeable containers. Dark amber glass containers with tight-fitting caps are required. Do not use containers with loose-fitting lids or glass stoppers. These may allow the introduction of air and result in peroxide formation.

d.    Label and test containers of peroxide formers in accordance with the details provided in Work Process P, Specific Controls and Procedures — Peroxide-Forming Compounds, and Work Process Y, Container Labeling. end flag

9.    Safe Storage Times

a.    Table P-1 of this program provides safe storage times and peroxide-testing frequencies.

b.    Peroxide-forming compounds may be safely stored for the indicated time periods. Storage for longer periods of time is allowable provided that testing is conducted at the indicated frequencies and that the results are within acceptable limits (see Work Process P.10, Peroxide Testing Method, below).

c.    Containers of unknown age or history, or those that have exceeded their shelf lives and that have no evidence of testing, should not be opened or disturbed. Contact the EHS industrial hygienist supporting your division for guidance.

10. Peroxide Testing Method

a.    start flagTesting and labeling (see below) are necessary to ensure the container can be safely handled. Testing frequency intervals are the same length as the indicated storage times.

b.    The testing method used at Berkeley Lab is the EM Quant® Peroxide Test Strip, 0-100 mg/l, or Baker Testrips for Peroxides 0-100 mg/l. These are available via the Laboratory's Procurement & Property website. (Note: the units: "mg/l" and "ppm" are equivalent in solution concentrations). These test strips contain the enzyme peroxidase, which transfers oxygen from the peroxide to an organic redox indicator, which is then converted to a blue oxidation product. Follow manufacturer’s instructions for testing and interpreting results.

c.    The Peroxide-Forming Chemical Appraisal Process for Divisions is a guide for researchers to evaluate their chemicals.

d.    The Peroxide-Forming Chemical Evaluation Sheet provides guidance to determine if a container is safe to open for testing.

e.    Although it has not been conclusively determined what concentration of peroxide is safe, the following rules should provide a reasonable margin of safety.

                                          i.    If the peroxide concentration is greater than 25 ppm, but less than 100 ppm, the chemical may be used, but DO NOT DISTILL OR CONCENTRATE.

                                         ii.    If the peroxide concentration is greater than or equal to 100 ppm, it should be disposed of as hazardous waste (see next section).

f.     Contact your division’s industrial hygienist if you have any doubt about the safety of opening and testing a container. end flag

11. Disposal

If a peroxide-forming compound has been stored beyond its useful shelf life, or if its age or history cannot be determined, it must be considered unsafe and should be disposed of as hazardous waste. Submit a Hazardous Waste Disposal Requisition Form to the EHS Waste Management Group. Write “Peroxide-forming Compound” on the form to alert EHS Waste Management Group to the potential hazard. Contact the industrial hygienist supporting your division if you have questions regarding safety. Waste disposal questions should be addressed to the EHS Waste Management Group.

12. Labeling

a.    All materials listed in Table P-1, as well as any other suspect peroxide former, should be dated when the container is received and when the container is first opened. A label for this purpose is available from the industrial hygienist who supports your division.

b.    The chemicals will be tested or disposed of according to the frequencies listed in Table P-1.

c.    Consult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers.

d.    Post the area entrance with a Caution Placard depicting hazards and emergency contact information.

13. Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spills and personal exposure to chemicals.

b.    In addition to these requirements, the following applies to spills of peroxide-forming compounds:

                                          i.    Do not attempt to clean up peroxide-former spills if there is any indication that these actions could initiate a detonation.

                                         ii.    Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills of peroxide formers. Keep an adequate number of appropriate spill kits to meet anticipated needs. These are commercially available through VWR Scientific. Typically, products containing diatomaceous earth are used for absorbing organic solvents.

                                        iii.    An emergency eyewash and safety shower should be located in all areas where laser dye and solvents are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment.

Work Process Q. Specific Controls and Procedures — Water-Reactive Chemicals

1.    General Information. Water-reactive chemicals react violently with water, releasing heat and, in some cases, explosive by-products. Of chief concern are the alkali metals. Alkali metals react vigorously with water to form hydroxide and gaseous hydrogen. The alkali metal-water reaction is exothermic. The heat generated can ignite the hydrogen gas. The rate of reaction and the hazard severity increase as atomic weight increases. Lithium reacts slowest and poses the least hazard. Rubidium and cesium react explosively. A DOE document, DOE-HDBK-1081-94, Primer on Spontaneous Heating and Pyrophoricity, provides additional information.

2.    Control Measures

a.    Work leads must identify water reactives used in the work area. Review sources such as MSDSs for specific compounds.

b.    An assessment of the hazards and controls in place is necessary to safeguard employees against these agents. Contact an EHS industrial hygienist to provide assistance.

c.    Most operations involving these materials require an AHD. This is determined by the using division in accordance with the provisions in the ES&H Manual Safe Work Authorizations program.

3.    Training and Information

a.    All employees who handle or may be exposed to water-reactive chemicals are required to attend Chemical Hygiene and Safety Training (EHS0348; or EHS0345 for Facilities personnel or 352 for summer students).

b.    These individuals should be trained in the specific hazards and controls of the water-reactives. This is a line management responsibility.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The area entrance should be posted with a Caution Placard depicting the hazards and emergency contact information.

4.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives (e.g., non-water-reactive chemicals) if possible.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System coordinator to assist you in finding a source of the chemical at Berkeley Lab.

c.    Conduct periodic clean-outs to prevent accumulating unneeded chemicals.

d.    Procure and use the minimum amount of material required for the operation, or

e.    Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.

f.     Enter these materials into the Chemical Management System (CMS).

5.    Engineering Controls. Alkali metals should be handled in a glove box made of materials that are compatible with the metal, with an inert gaseous atmosphere such as dry argon.

6.    Work Practices

a.    Do not eat; drink; smoke; chew gum; apply cosmetics; or store food, beverages, and tobacco products in work areas where water-reactive materials are being used.

b.    General traffic should be prohibited in areas where alkali metal operations are performed.

c.    Avoid all skin and eye contact with the material. Where possible, use tongs or appropriate tools to handle solids.

d.    All tools used to handle alkali metals must be dry, rust-free, clean, and composed of a material compatible with the metal. Tools can be dried by baking in an oven, desiccating in a vacuum, or rubbing with anhydrous dry soda ash.

e.    Oxidized materials (with a white surface coating) make the material more hazardous to handle because the oxide can flake off. NOTE: Materials with a yellow or orange coating may indicate the presence of peroxides, which may detonate if cut or abraded. Do not handle these materials. Contact an EHS industrial hygienist for further guidance.

f.     Assume that containers with alkali metals contain flammable hydrogen gas in the head space, even if stored under mineral oil or an inert gas. Thus, no source of ignition should be present where these containers are opened. Use nonsparking tools to open containers.

7.    Personal Protective Equipment (PPE). Skin and eye contact must be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

a.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed-toe shoes will be worn when handling these materials. For alkali metals, the shoes should be leather. This is to be considered as minimum protection and must be upgraded if necessary.

b.    Additional PPE such as chemical goggles, face shields, chemical aprons, fire-retardant aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

c.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

d.    Because many chemicals are skin-absorbers (i.e., agents that readily pass through the skin) it is important to select gloves that are chemically resistant to the material. Consult the PPE section, which contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

e.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

8.    Storage

a.   start flag Consult Work Process K, Chemical Storage, for hazardous material storage requirements, recommendations, and information on chemical incompatibility. It is recommended that alkali metals be stored in manufacturer-provided containers, if practical. Requirements for storing water-reactive chemicals are provided below.

b.    Separate alkali metals from incompatible chemicals. In addition to being water-reactive, alkali metals can react with oxygen, acids, halogenated hydrocarbons, and carbon dioxide.

c.    Store alkali metals under mineral oil or in an inert atmosphere. NOTE: Lithium may react with nitrogen to form nitrides. end flag

9.    Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spills and personal exposure to chemicals.

b.    In addition to these requirements, the following applies to spills of water-reactive compounds:

                                          i.    Never use combustible or reactive materials (such as paper towels) to clean up spills. Keep an adequate number of appropriate spill kits to meet anticipated needs.

                                         ii.    Anhydrous dry soda ash may be used for all metals except lithium. Lith-X fire extinguishers must be used for lithium. Met-L-X metal fire extinguishers may be used for sodium, potassium, and sodium-potassium (NaK) alloys. Employees involved in metal work must be trained in the use of these extinguishing materials.

                                        iii.    Only trained personnel should attempt to control small, contained fires or spills. If fumes escape into the breathing zone of these personnel, do not attempt to put out the fire. Large or unconfined fires or spills, or fires where the ventilation system does not contain all of the fumes, should be handled only by Fire Operations (7-911).

10. Skin or Eye Contact

a.    If any alkali metal fragment or drop enters the eye, it will immediately generate considerable heat, which is likely to result in severe eye injury. In such cases, the eyes should be flushed with water from an eyewash/safety shower. Continue to flush the eye with water while someone dials 7-911 for emergency help.

b.    When alkali metal comes in contact with the skin, remove all contaminated clothing. If contact with the metal occurs at only one or two spots on the skin, it is best to wash off those areas with mineral oil. A container with at least one quart of mineral oil should be available in alkali metal work areas labeled for this purpose. If contact with the metal is widely distributed over the body, a decision on the best course of first aid must be made immediately. If the material is already burning, the individual should be drenched continually under a safety shower until emergency help arrives. If the material is not burning, the metal should be removed by wiping the skin with mineral oil. In all cases, dial 7- 911 for assistance.

Work Process R. Specific Controls and Procedures — Pyrophoric Materials

1.    General Information

a.    Pyrophoric materials ignite spontaneously when exposed to air. Moreover, they are commonly associated with flammable solvents such as pentane, hexane, heptane, and diethyl ether. This combination poses a significant hazard to users. Other hazards posed by these materials include corrosivity, water reactivity, peroxide formation, and toxicity.

b.    A number of common reagents are pyrophoric, including (but not limited to):

                                          i.    Organolithium reagents. Typically in hydrocarbon solvents. Note: Tert-butyllithium solutions are highly pyrophoric.

                                         ii.    Organomagnesium reagents. These include Grignard reagents (RMgX). Typically in hydrocarbon solvents. Neat reagents are pyrophoric.

                                        iii.    Organoaluminum reagents. Neat or in hydrocarbon solvents. Neat reagents are highly pyrophoric.

                                       iv.    Organozinc reagents. Neat reagents are pyrophoric.

                                        v.    Boranes. Neat reagents are pyrophoric.

c.    Other pyrophoric liquids include metal alkyls such as trimethylaluminium, trimethylgalium, and trimethylindium.

d.    It is imperative that personnel understand the hazards associated with pyrophoric materials and their solvents, and understand how to control these hazards.

2.     Substitution and Chemical Inventory Management

a.    Prior to purchasing a pyrophoric material, users shall:

                                          i.    Review the hazards of the material and assess the conditions under which it will be used. Hazard information may be obtained from the MSDS or other information sources such as Bretherick’s Handbook of Chemical Reactive Hazards or by consulting with EHS industrial hygienists.

                                         ii.    Identify and use safer chemical alternatives if possible.

                                        iii.    Limit the amount purchased. As an alternative, consider borrowing what you need from a colleague in your group or contact the Chemical Management System Coordinator to assist you in finding a source of the chemical at Berkeley Lab.

                                       iv.    Enter pyrophoric materials into the Chemical Management System (CMS).

                                        v.    Keep working quantities to a minimum. Store and use the minimum for the operation. Then dispose of the excess.

                                       vi.    Not stockpile pyrophoric chemicals.

                                      vii.    Conduct periodic cleanouts to prevent accumulating unneeded pyrophoric chemicals.

3.    Activity Hazard Documents. Activity Hazard Documents (AHDs) are required for work involving pyrophoric material. An AHD is a formal work authorization that lists controls and procedures to reduce the risks associated with a higher-hazard activity to an acceptable level. A single AHD may be written for multiple operations or activities conducted in one or more areas, provided they are done under the same PI.

4.    Training and Qualifications

a.    Chemical Hygiene and Safety Training (EHS0348) and Fire Extinguisher Safety (EHS0520, EHS0522, and EHS0531) are required. However, because technique and handling practices are critical, on-the-job training (OJT) given by a knowledgeable, experienced worker, such as the work lead or AHD principal investigator shall be the primary training method. OJT must be documented in the AHD. The objectives of OJT are to ensure that users:

                                          i.    Understand the hazards of pyrophorics

                                         ii.    Understand the controls for pyrophorics

                                        iii.    Know, understand and use:

1.    Safe storage practices

2.    Labeling procedures. start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

3.    Safe handling practices, including transferring and use of equipment and apparatuses such as syringes and Schlenk lines

4.    Engineering controls

5.    Selection and use of PPE

5.    Emergency Procedures

a.    Users may work with pyrophoric materials unsupervised, provided that all of the following conditions are met:

                                          i.    OJT is completed and documented.

                                         ii.    The work lead has observed the user performing an unassisted procedure.

                                        iii.    The user has demonstrated proficiency in the safe handling and use of pyrophorics to the satisfaction of the work lead.

                                       iv.    Both the user and the work lead are confident that the user can perform the work safely.

6.    Safe Storage Methods

a.    start flagConsult Work Process K, Chemical Storage, for hazardous material storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below. end flag

b.    Store pyrophorics in an inert glove box. Pyrophoric materials and flammable liquids may be stored in the same inert glove box.

                                          i.    If storing in an inert glove box is not possible, keep pyrophorics in an airtight container and store in a flammable-storage locker specifically designated for pyrophorics. Pyrophoric materials and flammable liquids may not be stored together in the same flammable storage locker.

c.    Keep pyrophorics in their original containers (e.g., Sure/Seal bottles) unless experimental work requires transfer to other containers such as Straus flasks. Note: Sure/Seal bottles may leak when the septum is perforated. Therefore, inspect them on a regular basis and replace caps in an inert glove box if necessary.

d.    Pyrophoric materials may be stored in refrigerators designed and constructed for storing flammable liquids. However, the refrigerator(s) must be specifically designated for pyrophorics. Pyrophoric materials and flammable liquids may not be stored together in the same refrigerator. Consult the Work Process K, Chemical Storage, for additional requirements for refrigerators.

e.    Use secondary containment for all liquids.

7.    Handling, Transfer, and Use of Pyrophorics. All equipment in a pyrophoric reaction must be used following air-sensitive techniques:

a.    Oven-dry glassware used for pyrophorics.

b.    Flush glassware, syringes, and conveyance lines with argon or nitrogen.

c.    Use syringes equipped with Luer Locks to secure needles.

d.    Limit maximum volume that can be transferred with a syringe to 20 ml.

e.    Use cannulas for transferring larger volumes of pyrophorics.

f.     Clamp the reagent bottle and the receiving vessel to prevent tipping and to allow the free use of both hands.

g.    Conduct operations inside an inert glove box when possible.

h.    When it is not practical to use a glove box, conduct operations in a fume hood.

i.      Keep the sash of the hood to the lowest practical height.

j.     Glove boxes and fume hoods must have a current approval sticker.

k.    Keep flammable and combustible loading to a minimum in fume hoods and glove boxes. This includes reagents, paper, and cloth.

l.      More detailed descriptions may be found in The Manipulation of Air-Sensitive Compounds (Shriver and Drezdzon; John Wiley & Sons, New York, 1986), and in Aldrich Technical Bulletin AL-134, Handling Air-Sensitive Reagents, which is included with the purchase of air-sensitive chemicals and may be obtained from the Aldrich Technical Bulletins Web site.

8.    PPE and the Use of Nomex (fire-retardant) Lab Coats

a.    The minimum PPE for handling pyrophorics outside of inert glove boxes is: Nomex lab coat , safety glasses with side shields, long pants, closed toed shoes, and chemically resistant gloves. Disposable lab coats and lab coats made of polyester blends are prohibited for use with pyrophoric materials. If Nomex lab coats are not practical, a fire-retardant cotton lab coat may be used provided that a laundry is employed that is approved for laundering such garments in accordance with the manufacturer's requirements. Lab coats may be ordered and laundered through a service such as Mission Linen Supply.

b.    Cover goggles and/or face shields must be used as warranted by the hazard. Note: Face shields must be worn in conjunction with approved safety glasses or cover goggles. Consult Work Process I.6, Eye and Face Protection, or an EHS industrial hygienist for further guidance

c.    Glove selection will normally be based on the solvent containing the pyrophoric material. Consult Work Process I.5, Gloves, or an EHS industrial hygienist for further guidance.

9.    Emergency Procedures, including Extinguishing Media for Fires

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spills and personal exposure to chemicals.

b.    In addition to these requirements, the following applies to spills and fires involving pyrophoric compounds:

                                          i.    Safety must be the primary concern regarding spills. Do not attempt to clean up pyrophoric material spills that occur in an ambient atmosphere. Warn others, leave the area, and call the emergency number on the nearest safe lab phone (7-911 at Berkeley Lab).

                                         ii.    You may clean up spills in inert glove boxes only if it can be done safely.

                                        iii.    Avoid using combustible or reactive materials (such as paper towels) to clean up spills.

                                       iv.    Keep material on hand to absorb spills. Inorganic diatomaceous earth (Celite), clay-based kitty litter, and/or molecular sieves (13X) may be used. Ensure these materials are dry.

c.    Appropriate Class D fire extinguishers must be staged outside the work area. There are several different types of extinguishing media. Contact the Laboratory’s Fire Marshal for proper selection.

d.    If researchers choose to stage Class D fire extinguishers in the laboratory area, they will be responsible for performing the monthly inspections and for coordinating fire extinguisher service with Laboratory’s contractor. Contact the Laboratory’s Fire Marshal for guidance on selecting, staging, and inspecting fire extinguishers and for coordinating fire extinguisher services.

e.    If you use a fire extinguisher, ensure you empty the entire contents. As an option, plastic baggies of fire-extinguishing agent, such as Met-L-X or Lith-X, may be kept in inert glove boxes where the agent is appropriate for the material being handled. These baggies are not a substitute for the appropriate fire extinguisher but rather serve as a handy material to help extinguish a small fire. Employees must have OJT in the proper use of these extinguishing materials.

f.     Quench or otherwise neutralize spill clean-up materials prior to removing from the inert glove box.

g.    Only trained personnel may attempt to control small, contained fires or spills. If fumes escape into the breathing zone, do not attempt to put out the fire. Large or unconfined fires or spills, or fires where the ventilation system (glove box or fume hood) does not contain all of the fumes, must be handled by fire fighters. When in doubt, activate the nearest fire alarm and call the emergency number on the nearest safe lab phone (7-911 at Berkeley Lab).

10. Disposal

Information on waste disposal may be found in Guidelines for Generators to Meet HWHF Acceptance Requirements for Hazardous, Radioactive, and Mixed Wastes at Berkeley Lab Waste Generator Guidelines (PUB-3092). Only those who have completed Hazardous Waste Generator Training (EHS0604) are permitted to add waste to a Satellite Accumulation Area (SAA). Consult with the EHS Waste Generator Assistant who provides service to your division for guidance on the proper disposal of pyrophoric materials.

Work Process S. Specific Controls and Procedures — Engineered Nanomaterials

1.    General Information

a.    Engineered nanomaterials (ENMs) start flag(also known as engineered nanoparticles)end flag are defined as:

                                          i.    Materials having structures with at least one dimension between 1 and 100 nanometers (nm)

                                         ii.    Intentionally created, as opposed to those that are naturally or incidentally formed

b.    ENMs do not include:

                                          i.    Larger materials that may have nanoscale features, for example etched silicon wafers

                                         ii.    Biomolecules (proteins, nucleic acids, and carbohydrates)

                                        iii.    Materials with occupational exposure limits (OELs) that address nanosize particles for that substance

c.       start flagUnbound engineered nanoscale particles (UNPs) are defined as nanoscale particles that are not contained within a matrix under normal temperature and pressure conditions that would reasonably be expected to prevent the particles from being separately mobile and a potential source of exposure.

                                                              i.      An engineered primary nanoscale particle dispersed and fixed within a polymer matrix, incapable as a practical matter of becoming airborne, would be “bound,” while such a particle loosely attached to a surface (e.g., nanowire forest grown on wafer) or suspended in liquid (e.g., nanoparticles in colloidal suspension) or a dry powder would be “unbound.”

d.      A UNP worker is a worker who:

                                                              i.      Has the potential for inhalation of or dermal exposure to UNPs

                                                            ii.      Routinely spends time in an area in which engineered UNPs have the potential to become dispersed in the air or on surfaces or

                                                          iii.      Works on equipment that might contain or bear UNPs and that could release UNPs during servicing or maintenance end flag

e.       Exposures to ENMs may occur through inhalation, dermal contact, or ingestion start flagof UNPs.end flag Because of their tiny size, start flagUNPsend flag can penetrate deep into the lungs and may translocate to other organs following pathways not demonstrated in studies with larger particles.

f.     In general, laboratory personnel should treat all new compounds, including ENMs of unknown toxicity, as though they could be acutely toxic in the short run and chronically toxic over time. ENMs whose hazards have been studied should be managed in a manner consistent with the observed risks.

2.    Training and Information

a.    Employees who either handle or who may be exposed to the hazards of ENMs must indicate this on their Job Hazards Analysis (JHA), must complete Chemical Hygiene and Safety Training (EHS 348) and Safe Handling of Engineered Nanoscale Particulate Matter (EHS 344) and must comply with requirements listed in the JHA. 

b.    All employees in the work area must be trained in the specific hazards and controls of these materials. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

3.    Engineering Controls

a.    Conduct work that could generate start flagUNPsend flag in glove boxes, glove bags, laboratory fume hoods, or other negative-pressure or isolation enclosures. If a process (or subset of a process) cannot be enclosed, use other engineered systems to control fugitive emissions of start flagUNPsend flag or hazardous precursors that might be released. For example, use a local exhaust system such as a snorkel hood.

b.    With regard to gloves worn in glove boxes: Consider using an inner pair of different-color gloves to detect small tears in glove-box gloves and/or wearing an outer pair of gloves to prevent degradation of glove-box gloves. Refer to Work Process I, Personal Protective Equipment, for selecting chemically resistant gloves.

c.    Avoid exhausting effluent air reasonably suspected to contain start flagUNPsend flag whose hazards are not well understood. Whenever practical, filter it or otherwise clean (scrub) it before release. High Efficiency Particulate Arresting (HEPA) filtration appears to effectively remove start flagUNPsend flag from air.

d.    Do not use horizontal laminar-flow hoods (“clean benches”) that direct a flow of air into the laboratory to control exposure to start flagUNPsend flag.

e.    Consider exhausting Type II biological safety cabinets, in which free start flagUNPsend flag are handled, directly to the exterior (hard-ducted) or through a thimble connection over the cabinet’s exhaust.

f.     Evaluate laboratory equipment and exhaust systems for contamination before removing, remodeling, or repairing them.

4.    Housekeeping

a.    In so far as practicable, maintain all working surfaces (i.e., benches, glassware, apparatus, exhaust hoods, support equipment, etc.) free of start flagUNPend flag contamination. Some start flagUNPsend flag fluoresce under ultraviolet light, which can be useful in locating areas of contamination.

b.  Clean up dry start flagUNPsend flag using:

                                          i.    A dedicated HEPA vacuum-tested and certified by EHS

                                         ii.    Wet wiping

                                        iii.    Other methods that do not involve dry sweeping or the use of compressed air

c.    Dispose of used cleaning materials and wastes as hazardous waste (see below). 

5.    Chemical Inventory

a.    Enter all containers of commercially obtained ENMs into the Chemical Management System (CMS). The CMS has a check box for ENMs to allow easier identification of storage and use locations. Ensure this is checked when entering the material into the inventory. 

6.    Marking, Labeling, and Signage

a.    Post signs indicating hazards, minimum PPE requirements, and administrative control requirements at entry points into areas where ENMs are handled. Work Process AA, Posting Area Entrances, has specific posting requirements and instructions.

b.    Consult Work Process Y, Container Labeling, start flag for labeling requirements for primary and secondary containers.end flag Label containers to plainly indicate that the contents are in engineered nanoparticulate form, e.g., “nanoscale zinc oxide particles” or other identifier, rather than just “zinc oxide.”

c.    There may be practical limitations to carrying out these labeling requirements to small containers such as sample vials and tubes. Alternatives such as numbering or coding are permissible provided that the material’s identity and hazards are readily accessible (e.g., by means of a lab notebook, a spreadsheet, or some other equivalent means).

d.    When start flagUNPsend flag are being moved outside the work area, also include label text that indicates that the particulates may be unusually reactive and are potentially more toxic, quantitatively and qualitatively, than normal-scale forms of the same material.

7.    Storage

a.    start flagConsult Work Process K, Chemical Storage, for hazardous-materials storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below.

b.    Follow the storage guidelines in Work Process N, Specific Controls and Procedures — Flammables and Combustibles if the material is either flammable or combustible. end flag

8.    Personal Protective Equipment

a.    Skin and eye contact must be prevented. Wear PPE appropriate to the hazard, as identified through the Job Hazards Analysis process. Obtain a hazard assessment from an EHS industrial hygienist to determine the selection and use of PPE. PPE required for a wet-chemistry laboratory, which is often appropriate for handling ENMs, includes:

                                          i.    Laboratory coats

                                         ii.    Eye protection, e.g., safety glasses with side shields, face shields, chemical splash goggle, or other safety eyewear appropriate to the type and level of hazard. NOTE: Face shields or safety glasses alone do not provide sufficient protection against unbound, dry materials that could become airborne.

                                        iii.    Closed-toe shoes made of a low-permeability material

                                       iv.    Protective gloves

1.    Store gloves in a clean area outside of fume hoods and away from equipment that could potentially contaminate them.

2.    Wear polymer (e.g., nitrile rubber) gloves when handling ENMs and particulates in liquids. Choose gloves only after considering the resistance of the glove to the chemical attack both by the ENM and, if suspended or dissolved in liquid, the liquid. Consult the glove selection guides in Work Process I, Personal Protective Equipment. Disposable gloves may be appropriate

3.    Change gloves often to minimize potential exposure hazards. Alternatively, double-glove.

4.    For glove-box gloves: Consider using an inner pair of different-color gloves to detect small tears in glove-box gloves and/or wearing an outer pair of gloves to prevent degradation of glove-box gloves.

5.    Wash hands and forearms after wearing gloves.

b.    Keep potentially contaminated clothing and PPE in the laboratory or change-out area to prevent ENMs from being transported into common areas. Use disposable lab coats if feasible, and discard of them as hazardous waste (see below) when they become unusable. If cloth lab coats are used, do not send them to a laundry unless the laundry (such as the Berkeley Lab contract lab coat provider) has specifically agreed to handle ENM-contaminated clothing.

9.    Engineered Nanomaterial-Bearing Waste Streams

a.    Consider any material that has come into contact with start flagUNPsend flag (and that has not been decontaminated) as belonging to an ENM-bearing waste stream. This includes gloves, other PPE, wipes, blotters, and other disposable laboratory materials used during research activities.

b.    Do not put material from ENM-bearing waste streams into the regular trash or down the drain.

c.       Collect ENM-bearing waste in start flagan appropriate sealing container such as a plastic bag. Until the container is sealed, keep it in the laboratory hood. The container must remain sealed unless adding waste to it.end flag It should be managed as hazardous waste, including completing the Hazardous Waste label when accumulation begins, and placing it in an identified SAA. The identity of the waste must be given on the label. For example, “Wipes contaminated with trace levels of carbon nanotubes” provides an appropriate level of description. When the bag is full, close it, take it out of the hood, and place it into a second plastic bag or other sealing container in an SAA.

d.    Characterize and manage ENM-bearing waste streams per the requirements of the Berkeley Lab ES&H Manual Waste Management program. Be sure to consider the properties of all components, for example, solvents in which the ENMs may be dissolved or suspended.

10. Emergency Procedures and Spills

a.    Refer to Work Process V, Emergency Procedures and Equipment, for Berkeley Lab policy and response procedures for chemical spills. Spills containing ENMs are generally handled in a manner similar to spills of other potentially hazardous materials, with the following additional requirements:

                                          i.    Clean the spilled material using wet-wiping methods. Characterize, collect, and dispose of spill cleanup materials as ENM-bearing waste.

                                         ii.    Only HEPA vacuums that have been tested and certified by EHS may be used to vacuum nanomaterials. Do not dry-sweep or use compressed air.

                                        iii.    Consider using a walk-off mat such as a clean-room mat or “sticky mat” at access/egress points to reduce the likelihood of spreading nanoparticles. These are available through McMaster-Carr via the Laboratory’s Procurement & Property Web site.

Work Process T. Specific Controls and Procedures — Chemicals with Explosive Properties

1.    General Information

a.    Berkeley Lab staff periodically use chemicals with explosive properties (i.e., explosives).

b.    For activities such as bioremediation studies, in which the focus is on the materials’ chemical and physical properties as opposed to their explosive properties, Berkeley Lab does not conduct activities in which an explosion or fragmentation hazard exists. These include the synthesis, development, processing, blending, pressing, machining, testing, or detonation of explosives or assemblies containing explosives.

c.    An explosive is any chemical compound or mechanical mixture designed to undergo a very rapid chemical change with the evolution of large volumes of highly heated gases and that will deflagrate or detonate when subjected to heat, impact, friction, shock, or other suitable initiation stimuli.

                                          i.    Low explosives (see Figure 1) are materials that deflagrate: They burn more rapidly than materials undergoing normal combustion processes.

                                         ii.    High explosives detonate. Detonation is a process of combustion in which a shock wave is propagated at supersonic speeds. High explosives are divided into two classes: primary and secondary explosives.

1.    A primary explosive is extremely sensitive to impact, friction, heat, or electrostatic sources. Lead azide, lead styphnate, and mercury fulminate are examples of primary explosives. Primary explosives are often used in detonators or to trigger larger charges of less-sensitive secondary explosives. Primary explosives are prohibited at Berkeley Lab.

2.    Secondary explosives (also known as insensitive high explosives) are relatively insensitive to shock, friction, and heat. They may burn when exposed to heat or flame in small, unconfined quantities but normally require initiation from a primary explosive to detonate. Dynamite, trinitrotoluene (TNT), Cyclotrimethylenetrinitramine (RDX), Pentaerythritol tetranitrate (PETN), and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) are common secondary explosives.

d.    At Berkeley La, most explosives are used in dilute solutions. For explosives in solution concentrations ≤ 25% w/w, the main hazards are those associated with the solvent and the chemical as opposed to explosive properties of the material. However, if the solvent evaporates, or if the explosive crystallizes or precipitates, the primary hazard is associated with the explosive.

explosive categories

 

2.    Control Measures

a.    The following activities involving explosives are prohibited at Berkeley Lab:

                                          i.    Use of primary explosives

                                         ii.    Development, testing, processing, blending, pressing, and machining of explosives or assemblies containing explosives

                                        iii.    Operations that pose an explosion hazard, a metal fragment hazard, or a glass fragment hazard

b.    Work leads are responsible for identifying explosives used in the work area. Review sources such as MSDSs for specific compounds. 

c.    Any quantity of explosives, no matter how small, is hazardous. However, the risk from amounts ≤10 milligrams is significantly less than larger quantities. Therefore, quantities ≤10 mg require no special precautions other than following the requirements in the CHSP.

d.    Divisions shall do a risk assessment in consultation with an EHS Division subject matter expert for use of explosives in quantities >10 mg. A formal work authorization such as an AHD may be required. This is determined by the using division in accordance with the provisions in the ES&H Manual Safe Work Authorizations program.

e.    Airborne concentrations must be maintained at or below applicable occupational exposure limits, for the explosive and its solvent.

f.     Visiting scientists periodically bring solid secondary explosives (typically in gram quantities) to Berkeley Lab to study their mechanical properties. These activities must be coordinated with the host division; however, the transport, handling, use, security, and custody of the material must be overseen by the visitor’s explosives safety experts and Berkeley Lab Security and Emergency Operations. A written security plan must be developed by the visitors and approved by the hosting division and Berkeley Lab Security and Emergency Operations. Secondary explosives in quantities exceeding 10 grams are not permitted at Berkeley Lab.

3.    Training and Information

a.    Employees who either handle or who may be exposed to chemicals with explosive properties are required to complete Chemical Hygiene and Safety Training (EHS0348; or EHS0345 for Facilities personnel or 352 for summer students).

b.    All employees in the work area must be trained in the specific hazards and controls of the materials being handled. Area-specific training is a line management responsibility. EHS industrial hygienists are available to provide assistance.

c.    start flagConsult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers. end flag

d.    The entrance to the work area should be posted with a Caution Placard depicting hazards and emergency contact information.

4.    Substitution and Chemical Inventory Management

a.    Identify and use safer chemical alternatives (e.g., materials without explosive properties) if possible.

b.    If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System Coordinator to assist you in finding a source of the chemical at Berkeley Lab.

c.    Keep working quantities at or below 10 mg if possible. Don’t stockpile chemicals.

d.    Conduct periodic cleanouts to prevent accumulating unneeded chemicals.

e.    Procure and use the minimum amount of material required for the operation, or

f.     Enter these materials into the Chemical Management System (CMS).

5.    Ventilation

a.    Use a fume hood or other appropriate exhaust ventilation system when handling chemicals with explosive properties in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes procedures such as transfer operations, preparation of mixtures, blending, and sonification.

6.    Work Practices

a.    Maintain solution concentrations at or below 25% by weight whenever possible. At this concentration, the primary hazards are those associated with the solvent and not the explosive.

b.    Do not allow the compound to precipitate or crystallize.

c.    Control all ignition sources when handling explosives. This also applies to flammable and combustible solvents in which the material may be either dissolved or dispersed.

d.    Electrically bond and ground containers when transferring explosives that are either dissolved or dispersed in Class I flammable liquids and other flammable and combustible liquids at temperatures above their flash points.

e.    Storing and consumption of food is permitted in designated areas only. See Work Process J, Work Practice Controls, for additional information.

f.     Use a mechanical aid or a pipette bulb for pipetting.

g.    Open bottles or carboys slowly and carefully and wear protective equipment to guard hands, face, and body from splashes and vapors/gases.

h.    Wipe drips/residues from containers and work surfaces. Wash hands before leaving the work area and prior to consuming food/beverages.

7.    Personal Protective Equipment (PPE)

a.    Skin and eye contact must be prevented. Additional information may be found in Work Process T.7.c below.

b.    PPE shall be selected on the basis of the chemical hazard posed by the explosive compound and its solvent. PPE and shielding for protection against deflagration and detonation hazards should not be necessary because of the limits imposed on the types and quantities of explosives permitted and the stringent handling, storage and work practices required at Berkeley Lab.

c.    At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings), and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.

d.    Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves, and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS industrial hygienist may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial-hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.

e.    Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.

f.     Because many chemicals are skin-absorbers (i.e., agents that readily pass through the skin) it is important to select gloves that are chemically resistant to the material. Consult the PPE section. This contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.

g.    Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS industrial hygienist may also be contacted for assistance in selecting appropriate gloves.

8.    Storage

a.    start flag Consult Work Process K, Chemical Storage for hazardous-material storage requirements, recommendations, and information on chemical incompatibility. Because the type and quantity of explosives permitted at Berkeley Lab are restricted, the solvent in which the explosive is either dissolved or dispersed will be the main consideration with regard to storage. Additional requirements are provided below. end flag

b.    Follow the storage guidelines in Work Process N, Specific Controls and Procedures — Flammables and Combustible Liquids if the material is either flammable or combustible.

c.    Maintain solution concentrations at or below 25% by weight whenever possible. At this concentration, the primary hazards are those associated with the solvent and not the explosive.

d.    If several items of explosives in quantities ≤10 milligrams are present in one area, but the total inventory exceeds 10 mg, separate the items by placing them in individual drip trays or flammable-storage cabinets to prevent inadvertent combinations exceeding 10 milligrams total mass.

9.    Emergency Procedures

a.    Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spill and personal exposure to chemicals.

b.    If the solvent evaporates or if crystals or precipitates are visible, contact an EHS industrial hygienist for guidance. Avoid disturbing the container.

c.    In addition to these requirements, the following applies to flammable and combustible liquid spills:

                                          i.    Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills of flammable or combustible liquids. Keep an adequate number of appropriate spill kits to meet anticipated needs. These are commercially available through VWR Scientific. Typically, products containing diatomaceous earth are used for absorbing organic solvents.

d.    An emergency eyewash and safety shower should be located in all areas where flammable or combustible liquids are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment. See Work Process V.7.a, Emergency Eyewashes and Safety Showers.

Work Process U. Decommissioning Equipment, Buildings, Laboratories, and Shop Spaces

1.    Cleaning Prior to Transferring/Relocating Equipment or Vacating Laboratory and Shop Spaces. All surfaces and equipment should be cleaned and put into a safe condition prior to vacating, transferring, or relocating laboratory and shop spaces. The Laboratory’s Space Management Policy in the Requirements and Policies Manual requires that laboratory and shop spaces be cleared of debris and contamination prior to transfer of ownership. This is to safeguard the health and safety of Facilities, Transportation, and subcontractor personnel who work in these areas during space or building demolition, renovation, and construction. It also prevents delays in renovation and demolition schedules and minimizes costs to the divisions that own the space.

2.    Line Managers, PIs, and Supervisor Responsibilities

a.    Line managers, PIs, and supervisors of laboratory and shop spaces are the most familiar with the hazards, historical spills, contamination, etc., in their spaces and are therefore responsible for ensuring that chemical, physical, biological, and radiological hazards have been removed prior to releasing these spaces to Facilities or to new occupants.

b.    Contact an EHS industrial hygienist if assistance is needed with identifying hazards. In some cases, a separate hazard evaluation may be necessary.

3.    Facilities Responsibilities. For Facilities construction, renovation, or building-demolition projects, the Facilities Project Manager must ensure that these hazards have been removed by line managers, PIs, and supervisors of laboratory and shop spaces prior to turning the building or space over to the demolition/construction subcontractor. Building managers, division safety coordinators, and Facilities construction managers may be called upon to support this task.

4.    Areas to Be Decontaminated. Line managers, PIs, and supervisors of laboratory and shop spaces are responsible for removing visible residues, standing liquids, and loose particulate material (whether a known or unknown material) on floors, bench tops, and shelves; and inside drawers, cabinets, refrigerators, surfaces of local exhaust enclosures (e.g., chemical fume hood and biological safety cabinet), and any other potentially contaminated surfaces. This also applies to any equipment that is to be moved.

5.    Decontamination Processes

a.    It is recommended that surfaces be wiped down with mild detergents such as soap and water.

b.    A 10% bleach solution may be used for surfaces in labs where biological materials have been used.

c.    Use acid/alkaline neutralizers for acid or caustic spill areas.

d.    Contact EHS if mercury spills are detected to determine the appropriate spill-response actions. Attempting to clean up mercury spills may spread the contamination throughout a location or building. Stay in one location and call EHS for assistance, and warn others to stay out of the spill area/room.

6.    Who Can Perform Decontamination

a.    Laboratory and shop employees who have taken CHSP training (EHS0348 or 345) can generally perform this work. In certain cases, the amount of work may require using the services of an outside contractor, including trained hazardous-materials specialists or abatement workers. Berkeley Lab and subcontractor employees with OSHA Hazardous Waste Operations and Emergency Response (HAZWOPER) training, under the direction of a Berkeley Lab industrial hygienist, may also perform this work.

b.    Berkeley Lab custodians are not trained to perform this type of work; however, they may be contacted after the space has been evaluated and the room has been posted as being cleared by an EHS industrial hygienist (see section below).

c.    Contact an EHS industrial hygienist for assistance with this determination.

7.    Removal of Chemicals, Wastes, and Other Materials

a.    Equipment, supplies, products, and materials such as apparatuses, thermometers, gas cylinders, medical waste containers, sharps containers, sharps (needles and razor blades), trash, absorbent material, and other miscellaneous lab or shop material must be removed prior to vacating the space.

b.    For building demolitions, the project manager should be consulted to determine items that do not contain hazardous materials that are included in the demolition scope of work.

c.    In general, all chemicals and all chemical-related products must be removed. This includes cleaning compounds, surplus chemicals, stock solutions, experimental products, and hazardous waste located in Satellite Accumulation Areas (SAAs). A Waste Management Generator Assistance Specialist should be contacted for assistance.

8.    EHS Evaluation and Release of Laboratory and Shop Spaces

a.    Following the decontamination of work surfaces and the removal of chemical, physical, biological, and radiological hazards, EHS industrial hygienists and radiological control technicians (RCTs) will perform a final inspection prior to the release of the space, depending on the radiological use in the space.

b.    EHS industrial hygienists will evaluate the space for pH, evidence of debris, and “orphaned” chemicals and materials (as previously discussed), and will check for mercury in sink traps and floor surfaces.

c.    The radiological control technician will complete a green release tag indicating that the space has been cleared from radiological hazards (See the ES&H Manual Radiation Safety program). EHS industrial hygienists will release the space by posting the entrance (and individual pieces of equipment in some cases) with a release form that indicates the date and name of the industrial hygienist who evaluated the space.

d.    If individual pieces of equipment and supplies are to be moved to salvage or another building, and the owner of the equipment does not know whether hazardous materials are present, an EHS industrial hygienist may be contacted to evaluate these items and post them if they are safe to be handled by Berkeley Lab personnel or subcontractor employees.

Work Process V. Emergency Procedures and Equipment

1.    General Spill Response Procedures

a.    In the event of a chemical spill, follow the S.W.I.M.S. procedure:

                                          i.    STOP and think. Stop working. Stop the spill. Assess the situation:

1.    How big is the spill?

2.    Are there any injuries associated with the spill?

3.    Has it made contact with your skin or personal clothing?

4.    Can it be safely cleaned? NOTE: Follow the Spill Cleanup requirements listed below to make this determination.

                                        ii.    WARN others

1.    Call ext. 7911 or 9-911 if there is a medical emergency or danger to life, health or the environment.

2.    Alert people nearby.

                                       iii.    ISOLATE the area

1.    Restrict access to those involved in the spill cleanup.

2.    Determine the extent of the spill.

3.    Keep doors closed.

                                       iv.    MONITOR yourself carefully and completely

1.    Check yourself for any chemical contamination or signs/symptoms of exposure (e.g., wet clothing, skin or respiratory irritation).

2.    For medical emergencies, follow directions under the Emergency Preparedness: Emergency Response Guide.

                                        v.    STAY in or near the area until help arrives

1.    Minimize your movements. Avoid spreading contamination to other areas.

2.    Have a person who is knowledgeable about the incident be available to talk to or assist emergency personnel.

3.    Notify your work lead.

2.    Chemical Spill Cleanup Requirements

a.    You can clean up a chemical spill if ALL of the following requirements are met:

                                          i.    You are NOT a high school student or a guest participating in an internship program.

                                         ii.    There is no potential for release to the environment. NOTE: Care must be taken to avoid spreading or tracking chemical contamination to other areas.

                                        iii.    There are no personal injuries resulting from the spill.

                                       iv.    You know what the chemical hazards are.

                                        v.    The cleanup procedures are known and you have the proper spill-cleanup materials.

                                       vi.    You have the proper PPE to protect yourself during the cleanup.

                                      vii.    Two people can clean the spill up thoroughly within an hour.

                                     viii.    The spill does NOT involve elemental mercury. Special cleanup and monitoring procedures are required for mercury spills. Moreover, mercury contamination is easily tracked to other areas.

b.    If ALL of the above requirements are not met, or if you have any DOUBTS about your ability to safely and effectively clean up the spill, then:

                                          i.    Leave the immediate area,

                                         ii.    Close the door,

                                        iii.    Stay close by and control access. Post the entrance with a warning such as “Spill — Do Not Enter” and

                                       iv.    Call (or have someone call) ext. 6999 for assistance.

3.    Other Chemical Spill Cleanup Considerations

a.    General Requirements

                                          i.    Review these guidelines periodically — you must be familiar with them and know what to do before a spill occurs.

                                         ii.    Understand the hazards of the chemicals you use. Consult the Material Safety Data Sheets.

                                        iii.    Keep spill-cleanup kits in your work area.

1.    There are different types for acids, bases and solvents. These are commercially available through VWR Scientific. (The Laboratory has a contract with this vendor).

2.    It is important to note that absorbents and other materials used for spill cleanup need to be “inert” to the spilled material. For this reason, combustible materials such as sawdust and paper towels are generally inappropriate substitutes for the materials contained in spill kits.

                             &n