Department of Chemistry and Biochemistry

University of Wisconsin-La Crosse Chemical Hygiene Plan-2013

1.0 Purpose

2.0 Scope

3.0 Responsibilities

3.1 Chemical Hygiene Officer

3.2 Supervisors/Managers

3.3 Laboratory Assistants

4.0 Standard Operating Procedures for Laboratory Chemicals

4.1 Chemical Procurement

4.2 Chemical Storage

4.3 Chemical Handling

4.4 Laboratory Equipment and Glassware

4.5 Personal Protective Equipment

4.6 Personal Work Practices

4.7 Labeling

5.0 Criteria for Implementation of Control Measures

6.0 Fume Hood Management

7.0 Employee Information and Training

8.0 Required Notification and Approvals

9.0 Medical Consultation and Examination

10.0 Additional Protection

11.0 Emergency Response/Chemical Spills

12.0 Program Evaluation and Review

13.0 Suggested Chemical Storage Pattern

13.1 Inorganic

13.2 Organic

13.3 Additional Suggestions

Appendix Chapter 6D from Prudent Practices in the Laboratory, National Academy Press, 2011

1.0 Purpose

This Chemical Hygiene Plan (CHP) sets forth policies, procedures, equipment, personal protective equipment

and work practices that are capable of protecting employees from the health hazards presented by hazardous

chemicals used in laboratories. This CHP is intended to meet the requirements of 29 CFR 1910.1450,

Occupational Exposure to Hazardous Chemicals in Laboratories, including the non-mandatory Appendix A.

See http://ohsonline.com/articles/2013/01/21/osha-updates-guidance-on-hazardous-chemical-exposures-in-

labs.aspx?admgarea=news for the recent technical amendment to the Appendix.

2.0 Scope

This CHP applies to the University of Wisconsin-La Crosse Department of Chemistry and Biochemistry

Laboratories. The objective of this program is to provide guidance to all laboratory employees who use

hazardous chemicals, so that they can perform their work safely.

Laboratory Employee—This CHP applies to UW-L employees who work with hazardous chemicals in a

laboratory scale, where multiple procedures or chemicals are in use.

Frequenter—This standard does not apply to frequenters. Frequenters include students, UW-L employees and

others who have studies or work to perform in a laboratory. UW-L is required to provide a safe working or

learning environment for all frequenters. See also the Hazards Communication Program of UW-L.

3.0 Responsibilities

3.1 Chemical Hygiene Officer

Laura Roessler has been selected as the Chemical Hygiene Officer (CHO) for the CHP for the Department

of Chemistry and Biochemistry and will provide continued direction for the CHP for the next two fiscal

years (June 2013 through June 2015).

The Chemical Hygiene Officer shall:

1. Work with administrators, departmental faculty/staff through the Department of Chemistry and Biochemistry Safety Committee to develop and implement acceptable, appropriate chemical hygiene policies and practices,

2. Monitor procurement and use of chemicals in the lab, determining that laboratory facilities and training levels are adequate for chemicals in use,

3. Participate in regular, formal chemical hygiene and housekeeping inspections that include inspections of emergency equipment, personal protective equipment and engineering controls.

4. Direct the maintenance of a current chemical inventory of chemicals present within the UW-L Department of Chemistry and Biochemistry,

5. In consultation with the departmental safety committee and other faculty, review and improve the CHP on an annual basis,

6. Encourage department faculty and staff to fulfill their responsibilities for the safe operation of the Chemistry and Biochemistry Laboratories,

7. Work with the department safety committee to communicate and encourage laboratory employees to meet the requirements of this CHP,

8. Work with department faculty/staff to ensure the proper selection level of personal protective equipment.

9. Work with department faculty/staff to ensure that the appropriate training has been provided to employees,

10. Monitor the waste disposal program,

11. Manage access to lab spaces and chemical storage (keys, weekend use, etc.).

3.2 Supervisors/Managers

Supervisors are directly responsible for chemical hygiene in the laboratory. All laboratory instructors are

considered supervisors for the laboratory sections they teach. Principal Investigators (PIs) are responsible

for their own research labs. The supervisor/PI is required to ensure that provisions of the CHP are being

followed in the laboratory. Some teaching laboratories have a coordinator who will assist instructors in

ensuring that provisions of the CHP are being followed.

3.3 Student Laboratory Employees/Researchers

Laboratory teaching assistants, student workers who prepare chemicals and supplies for teaching laboratories, and students who work in the stockroom are expected to be familiar with the CHP and operate within its policies. This requirement also applies to any students who work in a Department of Chemistry and Biochemistry research laboratory under the direction of a PI. A training program shall be in place for these persons, which must be completed before work is started.

4.0 Standard Operating Procedures for Laboratory Chemicals

4.1 Chemical Procurement

The CHO should be informed of the decision to procure a chemical. A commitment of safe handling and

use of the chemical from initial receipt to ultimate disposal is expected.

UW-L’s policy is to regularly evaluate current chemical inventory and properly dispose of outdated or waste hazardous chemicals.

Information on proper handling, storage and disposal shall be identified by the purchaser prior to procurement of a chemical. In addition, chemicals used in the laboratory shall be those which are appropriate for the ventilation system. See the Laboratory Safety and Chemical Disposal Guide of the University of Wisconsin-La Crosse, 2002, for further information. A copy of this guide shall be physically present in the close vicinity of each laboratory. Copies can be obtained by contacting Dan Sweetman in the Environmental Health and Safety office.

All chemicals to be used in the Department of Chemistry and Biochemistry must either be delivered to the stockroom, or the CHO (or designee) should be notified that a Supervisor or PI has taken receipt.

Compressed gas cylinders are to be delivered to the separate storage area in Cowley Hall designed specifically for such cylinders, except that flammable gases are to be delivered straight to their point of use. The CHO will coordinate this.

When chemicals are received in the Department of Chemistry and Biochemistry, the pertinent instructor will be notified and a decision made as to whether the chemical should stay in the stockroom storage area or be moved to one of the laboratories for storage.

Chemical containers shall not be accepted without accompanying labels. If a Safety Data Sheet (SDS) previously called a Material Safety Data Sheet (MSDS), is not already available for the chemical, one shall be obtained. All containers of chemicals should be dated when received and dated again when opened.

4.2 Chemical Storage

Received chemicals shall be promptly moved to the designated Chemical Storage area by an instructor or

trained assistant. Large glass containers shall either remain in their original shipping container or be

placed in carrying containers (e.g., rubber "boots") during transportation.

All chemical storage areas shall be well-illuminated, with storage maintained at or below eye level. Flammables in excess of 10 gallons total per laboratory will be stowed in a flammable storage cabinet or in the specially designed flammable storage room within the chemistry and biochemistry stockroom.

Chemicals must be segregated by hazard classification and compatibility in a well-identified area, with good general exhaust ventilation.

Mineral acids should be segregated from flammable and combustible materials. Separation is defined by NFPA 49 as storage within the same fire area but separated by as much space as practicable or by intervening storage from incompatible materials.

Nitric acid will be stored in a secondary container large enough to hold the entire container contents. Acid resistant trays shall be placed under bottles of mineral acids.

Acid sensitive materials, such as cyanides and sulfides shall be separated from acids or protected from contact with acids and water.

Highly toxic chemicals or other chemicals whose containers have been compromised shall be stored in unbreakable secondary containers.

All flammable chemicals that should be refrigerated must be stored in a refrigerator/freezer which is rated for flammable storage. Ethers and other peroxide forming solvents should not be stored in a refrigerator.

A separate section in the compressed gas cylinder storage area shall be used for empty and full cylinders with appropriate signage. Cylinders should be used in rotation as received from the supplier. The storage area should be set up to permit proper inventory rotation. A special cart shall be provided to move the cylinders into their storage lanes and a separate cart provided to move a cylinder to its point of use and to move empty cylinders back to the main storage area. The valve-protection cap should be left on each cylinder until it has been secured against a wall or bench or placed in a cylinder stand, and is ready to be used. Avoid dragging, rolling, or sliding cylinders, even for a short distance. They should be moved by using a suitable hand truck.

Storage of chemicals at the lab bench or other work area shall be limited to those amounts necessary for one operation or shift. The amount of chemicals at the lab bench shall be as small as practicable.

Laboratory exhaust hoods should not be used to store chemicals that are not being immediately used in the procedure at hand.

Containers of chemicals should be kept closed when not in use.

The floor shall not be used to store chemicals.

Stored chemicals shall be examined at least annually by the CHO or a trained assistant for container integrity and/or deterioration. The inspection should determine whether any corrosion, deterioration, or damage has occurred to the storage facility as a result of leaking chemicals.

Periodic inventories of chemicals outside the chemistry stockroom area shall be conducted under the supervision of the Chemical Hygiene Officer. Unneeded items shall be properly discarded or returned to the chemistry stockroom storage area.

4.3 Chemical Handling

Each laboratory employee or student employee (with the training, education, and resources provided by

supervision), shall develop work habits consistent with requirements of the UW-L Department of Chemistry

and Biochemistry CHP to minimize potential personal and coworker exposure to chemicals. Based on the

realization that all chemicals inherently present hazards in certain conditions, exposure to all chemicals

shall be minimized.

General precautions which shall be followed for the handling and use of all chemicals are:

1. Skin contact with chemicals shall be avoided.

2. Employees shall wash all areas of exposed skin prior to leaving the laboratory. Hand soap is provided in each laboratory.

3. Mouth suction for pipetting or starting a siphon is prohibited.

4. Eating, drinking, smoking, chewing gum, or application of cosmetics in the laboratory is prohibited.

5. Storage of food or beverages is not allowed in storage areas or refrigerators used for laboratory operations.

6. Chemical mixtures which contain toxic component(s) shall be assumed to be toxic.

7. Substances of unknown toxicity shall be assumed to be toxic.

8. Laboratory employees/student employees shall be familiar with the symptoms of exposure for the chemicals which they work with and the precautions necessary to prevent exposure.

9. The intent and procedures of this CHP shall be continually adhered to.

10. For chemicals which have a Permissible Exposure Limit (PEL) from OSHA, engineering controls, followed by personal protective equipment shall be used to minimize any chance that these limits might be exceeded. The same standard applies to the Threshold Limit Values (TLV’s) set by the American Conference of Governmental Industrial Hygienists (ACGIH). A CD of these values is

available in the Chemistry and Biochemistry Stockroom. This additional requirement is part of the technical amendment of Appendix A of the OSHA Laboratory Standard and can be accessed here: http://ohsonline.com/articles/2013/01/21/osha-updates-guidance-on-hazardous-chemical-exposures-in-labs.aspx?admgarea=news

11. Engineering controls and safety equipment in the laboratory shall be utilized and inspected in accordance with guidelines established in the CHP.

12. An inspection log which documents eyewash/shower function will be maintained next to each installation. Eyewashes and showers will be tested at least once per month.

13. Specific precautions based on the toxicological characteristics of individual chemicals shall be implemented as deemed necessary by the CHO.

4.4 Laboratory Equipment and Glassware

Each employee/student employee shall keep the work area sufficiently clean and uncluttered as to prevent

personal contamination from touching the outside of a container or the lab bench or knocking over of

containers due to reaching or walking through the workspace.

Exits shall not be blocked on either side with furniture or equipment.

All chemicals shall be properly labeled, in accordance with UW-L’s CHP guidelines.

At the completion of each work day or operation, the work area shall be thoroughly cleaned and if

practical, equipment cleaned and stowed.

In addition, the following procedures shall apply to the use of laboratory equipment:

1. All laboratory equipment shall be used only for its intended purpose.

2. All glassware will be handled and stored with care to minimize breakage; all broken glassware will be immediately disposed of in the broken glass container.

3. All evacuated glass apparatus shall be shielded to contain chemicals and glass fragments should implosion occur.

4. Labels shall be attached to all chemical containers, identifying the contents and related hazards.

5. Waste receptacles shall be labeled as such.

6. All laboratory equipment shall be inspected on a periodic basis and replaced or repaired as necessary. Malfunctioning laboratory equipment shall not be used.

4.5 Personal Protective Equipment

Chemical splash goggles meeting ANSI Z87.1 are required for employees and frequenters to the

laboratory and will be worn at all times when corrosive or injurious chemicals are being used or

manipulated in the laboratory. A full face shield in addition to chemical splash goggles shall be worn

during certain chemical transfer and handling as procedures dictate. Such conditions exist but are not

limited to when handling corrosive, skin absorptive, cryogenic or pyrophoric hazardous chemicals.

Chemical resistant aprons or lab coats are strongly encouraged in the laboratory. Lab coats and goggles will be supplied to employees. They should be removed immediately upon discovery of significant contamination. Clean re–usable gloves after use to reduce permeation and degradation. Used gloves shall be inspected prior to use and replaced if damaged or deteriorated.

Thermal resistant gloves shall be worn for operations involving the handling of heated materials and exothermic reaction vessels. Thermal resistant gloves shall be non-asbestos and shall be replaced when damaged or deteriorated.

This CHP proscribes work that would require a respirator until such time as UW-L adopts a Respiratory Protection Plan. Dust masks can be used for comfort but the wearer must be informed of their limitations. In labs, respirators are not used because laboratory exhaust hoods and other engineering controls are preferentially installed and used.

4.6 Personal Work Practices

Laboratory supervision must ensure that each student knows and follows laboratory-specific rules and

procedures established by this plan.

All employees/students shall remain vigilant to unsafe practices and conditions in the laboratory and shall immediately report such practices and/or conditions to the laboratory supervisor. The supervisor must PROMPTLY correct unsafe practices or conditions.

Long hair or loose-fitting clothing shall be confined close to the body to avoid contact with chemicals or being caught in moving machine/equipment parts.

Only those hazardous chemicals appropriate for the ventilation system shall be used.

Avoid unnecessary exposure to all hazardous chemicals by any route.

Do not smell or taste any hazardous chemicals.

Encourage safe work practices for coworkers by setting the proper example. Rowdy behavior is strictly forbidden.

Seek information and advice from knowledgeable persons. Check standards and codes about the hazards present in the laboratory. Plan operations, equipment, and protective measures accordingly.

Use engineering controls in accordance with CHP procedures.

Inspect personal protective equipment prior to use, and wear appropriate protective equipment as procedures dictate and when necessary to avoid exposure.

4.7 Labeling

All containers not for the immediate use of an individual shall be labeled. This includes chemical

containers and waste containers. The labels shall be informative and durable, and at a minimum, will

identify contents, source, date of acquisition, and indication of hazard.

Peel and stick labels are available in the chemistry stockroom to be used for waste containers and for

portable containers filled from commercial bottles. Blank NFPA diamonds are printed on the labels used

for portable containers. The blanks should be filled in if possible using the information in the small

booklets that are available in each lab or from the information available in the chemistry stockroom.

Exemptions for labeling requirements shall be made for chemical transfers from a labeled container into a container which is intended only for the immediate use of the employee or student who performed the transfer.

Research samples whose identities are in question are also exempted from detailed labeling but must have a label that includes some reference to the method of preparation as designated by the PI.

Small student samples, unknown samples, etc. in teaching laboratories may be labeled using a code designated by the instructor but the instructor’s name should also be on the label.

The labeling program shall be periodically inspected by the Chemical Hygiene Officer to ensure that labels have not been defaced or removed.

5.0 Criteria for Implementation of Control Measures

A. When to use laboratory exhaust hoods:

Hoods should be used WHENEVER POSSIBLE to contain and exhaust hazardous dusts and volatile materials or other toxic or offensive materials. Processes that have potential for generating hazardous airborne chemical concentrations should be carried out within the fume hood.

B. When to use safety shields or other containment devices:

Safety shields must be used where the possibility exists for laboratory scale detonation or conflagration on exposure to air. Protective devices, such as long and short-handled tongs for holding or manipulating hazardous items should be used WHENEVER POSSIBLE.

C. When to use personal protective equipment—see section 4.5

D. When to institute special work practices:

Special work practices must be approved by the laboratory supervisor and the CHO. If particularly hazardous chemicals are to be used (e.g. carcinogens, reproductive toxins, teratogens, or acutely toxic chemicals), specific work practices and work locations must be designated. It is up to the laboratory supervisor to check the MSDS or other sources to determine if a particular chemical fits into this group. As a rule of thumb, if the LD50 is known, an acutely toxic chemical (ingestion) would be one with LD50 for rats ≤ 50 mg/kg body weight or if the LC50 is known (inhalation) an LC50 of ≤ 100 ppm . See http://www.ccohs.ca/oshanswers/chemicals/ld50.html for useful information on toxicity. See section 7.0 for other sources of information.

6.0 Laboratory Exhaust Hood Management

A. Frequency and type of monitoring - all local exhaust hoods used for primary containment control are continuously monitored for airflow.

B. Acceptable operating range - Face velocities between 85 and 120 linear fpm must be maintained for each hood. Face velocities outside these limits will cause an alarm to go off in the hood. If the face velocity cannot be adjusted to silence the alarm by adjusting the sash height while maintaining a usable opening then maintenance personnel must be contacted to repair or upgrade the hood.

C. Maintenance schedule - Maintenance of local exhausts or fume hoods will be completed on an "as needed" basis. Flow rate is to be inspected annually, with service coordinated by Facilities Planning and Management but paid by the local Department or College.

7.0 Employee Information and Training

A. Information

1. A copy of the OSHA Laboratory Standard, 29 CFR 1910.1450 is hereby referenced.

2. References to information on recommended exposure limits for other hazardous chemicals and

signs and symptoms associated with exposures to hazardous chemicals, material safety data

sheets, and other information on the hazards, safe handling, storage and disposal of hazardous

chemicals can be found in the Laboratory Safety and Chemical Disposal Guide, January 2002 found

in each chemistry and biochemistry laboratory. A copy can be obtained by contacting Dan

Sweetman in the Environmental Health and Safety office.

3. See http://www.osha.gov/SLTC/carcinogens/index.html for information on OSHA standards,

directives (instructions for compliance officers), and standard interpretations (official letters of

interpretation of the standards) related to carcinogens.

4. Also see the Report on Carcinogens, Twelfth Edition, 2011 from the U.S. Department of Health and

Human Services, the Public Health Service and the National Toxicology Program:

http://ntp.niehs.nih.gov/ntp/roc/twelfth/roc12.pdf

B. Training

1. Student researchers and all students who work in chemistry and biochemistry laboratories will be provided with training to ensure that they are apprised of the hazards of chemicals present in their work area. Such training will be provided at the time of their initial assignment to a work area where hazardous chemicals are present. Additional training will be provided as needed by supervisors. Initial training documentation, including the results of the required quiz will be collected and maintained by the Chemical Hygiene Officer or their designee.

a. Initial Student training will include: General Information: emergency contacts, resource information, legalities, regulatory agencies

b. Preventative Activities including attitude and Personal Protective Equipment (PPE) c. Chemical storage and disposal, including labeling and gas cylinders d. Documentation including reference books, SDS (MSDS) and the CHP e. Emergencies

2. Students in chemistry laboratory courses will receive safety training in conjunction with the course curriculum, as provided by the instructor. Documentation of this training will be maintained by the instructor or a Department of Chemistry and Biochemistry designee.

8.0 Required Notification and Approvals

If a laboratory supervisor or PI wishes to use a carcinogen, teratogen, mutagen, highly toxic or pyrophoric

chemical, the CHO must be notified and approve a written plan designed to protect laboratory personnel.

For pyrophoric chemicals, appropriate PPE must be provided to laboratory personnel. This would include a fire

resistant lab coat, fire resistant gloves and a face shield. These are available in the stockroom. An appropriate

fire extinguisher must be close at hand.

9.0 Medical Consultation and Examination

For specific State of Wisconsin regulations regarding the circumstances when exposure to hazardous

chemicals merits medical consultation and examination see the links below. Note the “department” is

defined as the Wisconsin Department of Workforce Development. These links are under the “Worker’s

Compensation Act. See http://dwd.wisconsin.gov/dwd/publications/wc/WKC-1-P.htm and access “Text of

Worker’s Compensation Act” or click on the following link:

http://dwd.wisconsin.gov/dwd/publications/wc/WKC_1_P_11/3%20Chapter_102.pdf and go to section

102.565, p. 92 and following.

A. Referencing these statutes, medical consultation and examination is appropriate for a laboratory

employee who works with hazardous chemicals and:

1. develops symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory

2. or is exposed to a hazardous chemical during a spill, leak, or explosion or other occurrence which might have resulted in exposure above OSHA’s Permissible Exposure Limit (PEL)

Under these circumstances, the employee is entitled to medical attention including an examination and follow-up exams as deemed necessary by the physician chosen by the employee.

3. To find PEL’s of hazardous chemicals see 29 CFR 1910.1000 of OSHA and subsequent sections

(tables Z-1, Z-2 and Z-3).

4. See the next sections (1910.1001 and 1910.1001 App A through App F) for specific rules and

PEL’s on asbestos, but primarily App G, H and I.

5. A later section (1910.1002) provides links regarding regulations of coal tar pitch volatiles.

6. See 1910.1003 at:

http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS&p_id=10007

for the restrictive regulations applying to the use of the following 13 select carcinogens:

4-Nitrobiphenyl, Chemical Abstracts Service Register Number (CAS No.) 92933;

alpha-Naphthylamine, CAS No. 134327;

methyl chloromethyl ether, CAS No. 107302;

3,3'-Dichlorobenzidine (and its salts) CAS No. 91941;

bis-Chloromethyl ether, CAS No. 542881;

beta-Naphthylamine, CAS No. 91598;

Benzidine, CAS No. 92875;

4-Aminodiphenyl, CAS No. 92671;

Ethyleneimine, CAS No. 151564;

beta-Propiolactone, CAS No. 57578;

2-Acetylaminofluorene, CAS No. 53963;

4-Dimethylaminoazo-benzene, CAS No. 60117; and

N-Nitrosodimethylamine, CAS No. 62759.

B. Procedures to secure medical consultation and examination are as follows:

1. Report exposure to CHO.

2. Seek medical care at a health care center of the employee's choice. (Students are not covered by

this CHP but are encouraged to use Student Health Services.)

3. The employer or affected employee will provide the following information to the physician.

a. Identity of hazardous chemical

b. Description of conditions under which exposure occurred

c. Description of signs and symptoms employee or student is experiencing

4. A written opinion from the physician shall be provided to the employer including:

a. Recommendation for further medical follow-up

b. Results of medical exam and tests

c. Any medical condition revealed during the exam that places the employee or student at

increased risk

d. A statement that the employee or student has been informed by the physician of the results of

the exam and any medical condition that may require further treatment or examination

10.0 Additional Protection

A. Work with select carcinogens, reproductive toxins and substances that have a high degree of acute

toxicity may require additional employee or student protection. See Appendix D of the Laboratory Safety

and Chemical Disposal Guide, January 2002, for definitions of particularly hazardous substances. A

copy can be obtained by contacting Dan Sweetman in the Environmental Health and Safety office if

your laboratory does not have one. Specific consideration will be given to:

1. Use of containment devices such as laboratory exhaust hoods or glove boxes.

2. Procedures for safe removal of contaminated waste.

3. Decontamination procedures.

4. See CFR 1910.1003 and subsequent sections through 1910.1016 at: http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS&p_id=10007 for the restrictive regulations applying to the use of the following 13 select carcinogens: 4-

Nitrobiphenyl, Chemical Abstracts Service Register Number (CAS No.) 92933; alpha-Naphthylamine, CAS No. 134327; methyl chloromethyl ether, CAS No. 107302; 3,3'-Dichlorobenzidine (and its salts) CAS No. 91941; bis-Chloromethyl ether, CAS No. 542881; beta-Naphthylamine, CAS No. 91598; Benzidine, CAS No. 92875; 4-Aminodiphenyl, CAS No. 92671; Ethyleneimine, CAS No. 151564; beta-Propiolactone, CAS No. 57578; 2-Acetylaminofluorene, CAS No. 53963; 4-Dimethylaminoazo-benzene, CAS No. 60117; and N-Nitrosodimethylamine, CAS No. 62759.

Regulations for certain of these substances require respirator protection and decontamination of external exhaust air. The Department of Chemistry and Biochemistry does not have this capability at the present time.

5. Section 1910.1017 and App A deals with the cancer hazards and regulations regarding vinyl chloride.

6. Section 1910.1018 and App A deals with cancer and other hazards and regulations regarding inorganic arsenic.

7. Section 1910.1020 deals with the regulations regarding the right of employees to have access to employee exposure or medical records.

8. Section 1910.1020 App A describes the Registry of Toxic Effects of Chemical Substances (RTECS) list from NIOSH which can be purchased. To quote an excerpt from this document:

"In this edition of the Registry, the editors intend to identify "all known toxic substances" which may exist in the environment and to provide pertinent data on the toxic effects from known doses entering an organism by any route described.(p xi)

"It must be reemphasized that the entry of a substance in the Registry does not automatically mean that it must be avoided. A listing does mean, however, that the substance has the documented potential of being harmful if misused, and care must be exercised to prevent tragic consequences. Thus the Registry lists many substances that are common in everyday life and are in nearly every household in the United States. One can name a variety of such dangerous substances: prescription and non-prescription drugs; food additives; pesticide concentrates, sprays, and dusts; fungicides; herbicides, paints; glazes, dyes; bleaches and other household cleaning agents; alkalis; and various solvents and diluents. The list is extensive because chemicals have become an integral part of our existence."

The RTECS printed edition may be purchased from the Superintendent of Documents, U.S. Government Printing Office (GPO), Washington, DC 20402 (202-783-3238).

9. See http://www.cdc.gov/niosh/npg/default.html for the NIOSH Pocket Guide to Chemical Hazards. “The NIOSH Pocket Guide to Chemical Hazards (NPG) is intended as a source of general industrial hygiene information on several hundred chemicals/classes for workers, employers, and occupational

health professionals. The NPG does not contain an analysis of all pertinent data, rather it presents key information and data in abbreviated or tabular form for chemicals or substance groupings (e.g. cyanides, fluorides, manganese compounds) that are found in the work environment. The information found in the NPG should help users recognize and control occupational chemical hazards.”

B. Operating procedures that are at least as protective as those described in chapter 5 D Prudent Practices

in the Laboratory, National Academy Press, 1995, (Working with Substances of High Toxicity), will be

employed for work with particularly hazardous substances. This section is excerpted as an Appendix

below. A free pdf copy of the 2011 version of this book is available at

http://www.nap.edu/catalog.php?record_id=12654 .

11.0 Emergency Response/Chemical Spills

All Chemistry and Biochemistry instructors should be familiar with the UW-L Emergency Response and Preparedness Plan. See http://www.uwlax.edu/police/emerg.htm as well as section E of the Laboratory Safety and Chemical Disposal Guide, January 2002 found in each chemistry and biochemistry laboratory. A copy can be obtained by contacting Dan Sweetman in the Environmental Health and Safety office.

When chemical spills occur within the Laboratory, the following procedures are followed to prevent injury or property loss: This information is also found in section E of the Laboratory Safety and Chemical Disposal Guide, January 2002 found in each chemistry and biochemistry laboratory. A copy can be obtained by contacting Dan Sweetman in the Environmental Health and Safety office. See especially the UW-L Hazardous Material Spill Response Decision Chart, section E, p. 9.

A. Spill Procedures

1. Notify area occupants and supervisor of the spill. All spills must be reported to a supervisor no

matter how small. An incident report should be filled out after the incident is dealt with.

2. If the spill is larger than the amount normally worked with, spreads rapidly or endangers people or

property except by direct contact do not attempt cleanup but evacuate the laboratory and get help.

You may contact a supervisor or the Chemical Hygiene Officer but for a possibly life threatening

situation call University Police at 608-789-9999 or 911. The La Crosse Fire Department’s

Hazardous Materials Response Team can provide help if needed.

3. Even a small amount of spilled flammable liquid or reactive substance presents a significant fire

hazard. There are many spark sources in laboratories. Do not hesitate to evacuate, notify 911 or

University Police and pull the fire alarm if you are unsure of the spill’s fire potential.

4. Check for personal contamination and if trained, provide any first aid necessary to affected

personnel. Liberally use eyewash station and/or safety shower to flush affected areas. Industry

standard recommendations include flushing affected area for AT LEAST 15 minutes. The use of the

eyewash or safety shower merits follow up consultation with a physician. Depending on the severity

of contamination students may use Student Health Services or a 911 call may be needed. Other

employees may use their own physicians or the emergency room associated with their health

coverage. Again, a 911 call may be advisable.

5. Any uncontained chemical that can disperse fumes, gases or dusts may be hazardous to your

health and the health of those around you. If you suspect that the spilled or released chemical is

toxic, evacuate the area. If others in the area could be exposed to the chemical, evacuate the area

or building. University Police can activate an evacuation alarm.

6. Avoid all contact with spilled material. If the spill is small enough to attempt clean up, use protective

gloves, lab coat or apron and chemical splash goggles.

7. Always refer to MSDS for special precautions or spill cleanup requirements.

8. Obtain supplies from Chemical Spill Clean-Up Kit.

9. Contain collected materials and label container with name of contents and also as Hazardous

Waste.

B. Liquid Spills

1. Confine spill to small area as practical. 2. For small quantities of acids or bases, use the neutralizing agent from the chemical spill clean-up kit.

An absorbent material specially prepared for acid/base spills may also be used. 3. For small quantities of other materials, such as organic solvents, utilize an absorbent material to

clean-up spill. There are “spill pillows” available in the spill kit for this. An example of an absorbent material which may be used is a clay-type kitty litter.

4. For large quantities of inorganic acids and bases consult the CHO or a supervisor. 5. Carefully pick up and decontaminate any bottles, broken glass, and/or other containers.

Decontaminate over the bucket or pail to collect contaminated wash. 6. Avoid using any shop vacuum which is not rated for chemical clean-up. A potential exists for

atomizing hazardous wastes and creating a potential human inhalation exposure. 7. If the spill is extremely volatile (high vapor pressure) AND THERE ARE NO IGNITION SOURCES IN

THE LAB, allow the spill to evaporate and exhaust out the laboratory exhaust (e.g., laboratory exhaust hood).

8. Properly containerize, label, store and/or dispose of collected hazardous waste. (See waste disposal

section G of the UW-L Laboratory and Chemical Disposal Guide for methods).

C. Solid Spills

If possible, sweep solid spills of low toxicity into a designated, easily decontaminated, dust pan and place

in a labeled container for storage and/or disposal.

D. Additional Spills

Mercury -- Clean-up with pre-purchased spill clean-up kit. Collect Hg in a sealed container to prevent exposure to Hg vapors. Large spills or spills that render some Hg unavailable for clean-up (e.g., Hg in floor cracks or beneath lab benches), an airborne evaluation of Hg vapor content may be required. Elemental mercury has been nearly eliminated from the UW-L campus. Report the continued possession of mercury-containing equipment to the CHO and to Dan Sweetman in the Environmental Health and Safety office.

E. Compressed Gas Cylinders

Any compressed gas cylinders used in chemistry and biochemistry laboratories must be strapped down

during use and in storage. They must be transported with the cylinder cap in place while strapped to a

handcart.

F. Incident Report

An incident investigation should take place after each spill and/or accident. The Risk Management office should be notified any time an incident occurs that results in any of the following:

Property damage or personal injury to any individual on UW-L property.

Property damage or personal injury to any individual in connection with an event or activity sponsored or organized by UW-L or any UW-L department or organization, regardless of location.

Breach of security or unauthorized access to any university property or assets (including electronic systems or data).

Violation of law or monetary liability (actual or potential) on the part of the university or on the part of any individual acting in the scope of their employment with the university.

The first step in this process is for the individual(s) with knowledge of the incident to complete an Incident Report, using either the online form or the paper form, both of which are accessible using the links which follow link. (If multiple people have independent knowledge of the incident, each one is requested to complete their own incident report.) No personal information submitted using either the online form or the written form will be used for any purpose other than investigating the incident. An Incident Report form may be obtained at:

http://www.uwlax.edu/budgetandfinance/riskmanagement/incidentreport.htm

and should be completed and given to the CHO.

A different form is required for employees who might be entitled to Workman’s Compensation. See

http://www.uwlax.edu/hr/current/accidents_workers_comp.htm for appropriate forms and procedures.

12.0 Program Evaluation and Review

The Chemistry and Biochemistry Department Safety Committee in cooperation with the Chemical

Hygiene Officer is responsible for annually reviewing this program, its effectiveness, and for updating

as needed.

This Program was adopted: May 1, 2013.

13.0 Suggested Chemical Storage Pattern

Strictly alphabetical storage of chemicals often leads to mutually incompatible or reactive chemicals

being stored in close proximity, increasing the potential for violent reaction in the event of breakage.

13.1 Inorganic, organized by compatibility classes

1. Metals, Hydrides 2. Acetates, Halides, Iodides, Sulfates, Sulfites, Halogens, Thiosulfates, Phosphates 3. Amides, Nitrates (except Ammonium Nitrate), Nitrites, Azides 4. Hydroxides, Oxides, Silicates, Carbonates, Carbon 5. Sufides, Selenides, Phosphides, Carbides, Nitrides 6. Bromates, Perchlorates, Perchloric Acid, Chlorites, Hypochlorites, Peroxides, Hydrogen Peroxide

7. Arsenates, Cyanides, Cyanates 8. Borates, Chromates, Manganates, Permanganates 9. Acids (except Nitric). Store acids in a designated cabinet. *Nitric Acid is isolated and stored by

itself. 10. Sulfur, Phosphorus, Arsenic, Phosphorus Pentoxide.

13.2 Organic, organized by compatibility classes

1. Acids, Anhydrides, Peracids 2. Alcohols, Glycols, Amines, Amides, Imines, Imides 3. Hydrocarbons, Esters, Aldehydes 4. Esters, Ketones, Ketenes, Halogenated Hydrocarbons, Ethylene Oxide 5. Epoxy Compounds, Iso-cyanates 6. Peroxides, Hydroperoxides, Azides 7. Sulfides, Polysulfides, Sulfoxides, Nitriles 8. Phenols, Cresols

13.3 Additional Suggestions 1. Avoid floor chemical storage (even temporary). 2. No hazardous chemical stored above eye level. 3. Shelf assemblies are firmly secured to walls. Avoid island shelf assemblies. 4. Provide anti-roll-off lips on all shelves. 5. Ideally shelving assemblies would be of wood construction. 6. Avoid metal, adjustable shelf supports and clips. Better fixed, wooden supports. 7. Store acids in dedicated acid cabinet(s). Store Nitric Acid in that same cabinet ONLY if isolated

from other acids. Store flammables in a dedicated flammables cabinet. 8. Store severe poisons in a dedicated poisons cabinet. 9. If you store Class A or Class B flammables in a refrigerator, the refrigerator must be rated for

flammable storage. The thermostat switch or light switch in a standard refrigerator may spark and set off the volatile vapors in the refrigerator and cause an explosion.

Appendix:

Chapter 6D Prudent Practices in the Laboratory, National Academy Press, 2011

6.D WORKING WITH SUBSTANCES OF HIGH TOXICITY Individuals who work with highly toxic chemicals, as identified in Chapter 4 (see section 4.C, Tables 4.1, 4.2, and 4.3), should be thoroughly familiar with the general guidelines for the safe handling of chemicals in laboratories (see section 6.C). They should also have acquired through training and experience the knowledge, skill, and discipline to carry out safe laboratory practices consistently. However, these guidelines alone are not sufficient when handling substances that are known to be highly toxic and chemicals that, when combined in an experimental reaction, may generate highly toxic substances or produce new substances with the potential for high toxicity. Additional precautions are needed to set up multiple lines of defense to minimize the risks posed by these substances. As discussed in section 6.B, preparations for handling highly toxic substances must include sound and thorough planning of the experiment, an understanding of the intrinsic hazards of the substances and the risks of exposure inherent in the planned processes, selection of additional precautions that may be necessary to minimize or eliminate these risks, and review of all emergency procedures to ensure appropriate response to unexpected spills and accidents. Each experiment must be evaluated individually because assessment of the level of risk depends on how the substance will be used. Therefore, a prudent planner does not rely solely on a list of highly toxic chemicals to determine the level of the risk; under certain conditions, chemicals not on these lists may react to form highly toxic substances. In general, the guidelines in section 6.C reflect the minimum standards for handling hazardous substances and should become standard practice when handling highly toxic substances. For example, although working alone in laboratories should be avoided, it is essential that more than one person be present when highly toxic materials are handled. All people working in the area must be familiar with the hazards of the experiments being conducted and with the appropriate emergency response procedures. Use engineering controls to minimize the possibility of exposure (see section 6.D.5). The use of appropriate PPE to safeguard the hands, forearms, and face from exposure to chemicals is essential in handling highly toxic materials. Cleanliness, order, and general good housekeeping practices create an intrinsically safer workplace. Compliance with safety rules should be maintained scrupulously in areas where highly toxic substances are handled. Source reduction is always a prudent practice, but in the case of highly toxic chemicals it may mean the difference between working with toxicologically dangerous amounts of materials and working with quantities that can be handled safely with routine practice. Emergency response planning and training are very important when working with highly toxic compounds. Additional hazards from these materials (e.g., flammability and high vapor pressures) can complicate the situation, making operational safety all the more important. 6.D.1 Planning Careful planning should precede any experiment involving a highly toxic substance whenever the substance is to be used for the first time or whenever an experienced user carries out a new protocol that increases the risk of exposure substantially. Planning should include consultations with colleagues who have experience in handling the substance safely and in protocols of use. Experts in the institution’s EHS program are a valuable source of information on the hazardous properties of chemicals and safe practice. They also need to be consulted for guidance regarding those chemicals that are regulated by federal, state, and local agencies or by institutional policy. Thoroughly review the wealth of information available in the MSDS, the literature, and toxicological and safety references. When planning, always consider substituting less toxic substances for highly toxic ones. Also, be sure to use the smallest amount of material that is practicable for the conduct of the experiment. Other important factors to be considered in determining the need for additional safeguards are the likelihood of exposure inherent in the proposed experimental process, the toxicological and physical properties of the chemical substances being used, the concentrations and amounts involved, the duration of exposure, and known toxicological effects. Plan for careful management of the substances throughout their life cycle—from acquisition and storage through destruction or safe disposal. Document these plans, and review them with personnel doing the work, as well as others in the laboratory. Finally, include a method for receiving feedback that can be incorporated into policy revisions, allowing for continuous improvement of the procedures. 6.D.2 Experiment Protocols Involving Highly Toxic Chemicals Before the experiment begins, prepare an experiment plan that describes the additional safeguards that will be used for all phases of the experiment from acquisition of the chemical to its final safe disposal. The amounts of materials used and the names of the people involved should be included in the written summary and recorded

in the laboratory notebook. The planning process may demonstrate that monitoring is necessary to ensure the safety of the experimenters. Such a determination is made when there is reason to believe that exposure levels for the substances planned to be used could exceed OSHA-established regulatory action levels, similar guidelines established by other authoritative organizations, or when the exposure level is uncertain. People who conduct the work should know the signs and symptoms of acute and chronic exposure, including delayed effects. Arrange ready access to an occupational health physician, and consult with the physician to determine if health screening or medical surveillance is appropriate. 6.D.3 Designated Areas Experimental procedures involving highly toxic chemicals, including their transfer from storage containers to reaction vessels, should be confined to a designated work area in the laboratory. This area, which may be a laboratory chemical hood or glovebox, a portion of a laboratory, or the entire laboratory module, should be recognized by everyone in the laboratory or institution as a place where special training, precautions, laboratory skill, and safety discipline are required. Post signs conspicuously to indicate the designated areas. It may also be prudent to post any relevant LCSS outside the laboratory door. The designated area may be used for other purposes, as long as all laboratory personnel comply with training, safety, and security requirements, and they are familiar with the emergency response protocols of the institution. In consultation with the institution’s EHS experts, the laboratory supervisor should determine which procedures and highly toxic chemicals need to be confined to designated areas. The general guidelines (section 6.C) for handling hazardous chemicals in laboratories may be sufficient for procedures involving very low concentrations and small amounts of highly toxic chemicals, depending on the experiment, the reagents, and their toxicological and physical properties. 6.D.4 Access Control Restrict access to laboratories where highly toxic chemicals are in use to personnel who are authorized for this laboratory work and trained in the special precautions that apply. Administrative procedures or even physical barriers may be required to prevent unauthorized personnel from entering these laboratories. Keep laboratory doors closed and locked to limit access to unattended areas where highly toxic materials are stored or routinely handled. However, security measures must not prevent emergency exits from the laboratory. Be sure to make special arrangements for emergency response, including after normal work hours. Use locks to secure refrigerators, freezers, and other storage areas. Keep track of authorized personnel, and be sure to retrieve keys and change locks and access when these people no longer work in the area. Keep a detailed inventory of highly toxic chemicals. The date, amount, location, and responsible individual should be recorded for all acquisitions, syntheses, access, use, transport, distribution to others, and disposal. Perform a physical inventory every year to verify active inventory records. A procedure should be in place to report security breaches, inventory discrepancies, losses, diversions, or suspected thefts. When long-term experiments involving highly toxic compounds require unattended operations, securing the laboratory from access by untrained personnel is essential. These operations should also include failsafe backup options such as shutoff devices in case a reaction overheats or pressure builds up. Additionally, equipment should include interlocks that shut down experiments by turning off devices such as heating baths or reagent pumps, or that close solenoid valves if cooling water stops flowing through an apparatus or if airflow through a laboratory chemical hood becomes restricted or stops. An interlock should be constructed in such a way that if a problem develops, it places the experiment in a safer mode and will not reset even if the hazardous condition is reversed. Protective devices should include alarms that indicate their activation. Security guards and untrained personnel should never be asked or allowed to check on the status of unattended experiments involving highly toxic materials. Warning signs on locked doors should list the trained laboratory personnel to be contacted in case an alarm sounds within the laboratory. 6.D.5 Special Precautions for Minimizing Exposure to Highly Toxic Chemicals The practices listed below help establish the necessary precautions to enable laboratory work with highly toxic chemicals to be conducted safely: 1. Conduct procedures involving highly toxic chemicals that can generate dust, vapors, or aerosols in a laboratory chemical hood, glovebox, or other suitable containment device. Check hoods for acceptable operation prior to conducting experiments with toxic chemicals. If experiments are to be ongoing over a significant period of time, the hood should be rechecked at least quarterly for proper operation and be equipped with flow-sensing devices that show at a glance or by an audible signal whether they are performing adequately. When toxic chemicals are used in a glovebox, it should be operated under negative pressure, and the gloves should be checked for integrity and appropriate composition before use. Consider if reactive or toxic effluents may be generated by the procedure. If so, scrubbing may be necessary. If dusts or aerosols are generated, consider using high-efficiency particulate air (HEPA) filters prior to discharge to the atmosphere. Hoods should not be used as waste disposal devices, particularly when toxic substances are

involved. To offer maximum protection, they should be operated with sashes at their proper level whenever possible. Monitoring equipment might include both active and passive devices to sample laboratory working environments. The experimenter must ensure that the hood exhaust will not present a hazard to anyone outside the immediate laboratory environment. For instance, rooftop access may need to be eliminated during certain operations or, when rooftop access is required, work with highly toxic materials must not be allowed. (See Chapter 9, section 9.C, for detailed discussion on laboratory chemical hoods and environmental control.) When available, alarmed detection devices are another engineering control that should be used for highly toxic materials. Air dispersion modeling may be necessary to determine if exhaust ventilation will affect nearby air intakes or other sensitive receptors. 2. Gloves must be worn when working with toxic liquids or solids to protect the hands and forearms. Select gloves carefully to ensure that they are impervious to the chemicals being used and are of correct thickness to allow reasonable dexterity while also ensuring adequate barrier protection. (See section 6.C.2.6.1 for more information on gloves.) 3. Face and eye protection is necessary to prevent ingestion, inhalation, and skin absorption of toxic chemicals. Safety glasses with side shields are a minimum standard for all laboratory work. When using toxic substances that could generate vapors, aerosols, or dusts, additional levels of protection, including full-face shields and respirators, are appropriate, depending on the degree of hazard represented. Transparent explosion shields in hoods offer additional protection from splashes. Medical certification, training, and fittesting are required if respirators are worn. 4. Equipment used for the handling of highly toxic chemicals should be isolated from the general laboratory environment. Consider venting laboratory vacuum pumps used with these substances via high-efficiency scrubbers or an exhaust hood. Motor-driven vacuum pumps are recommended because they are easy to decontaminate (decontamination should be conducted in a designated hood). 5. Always practice good laboratory hygiene where highly toxic chemicals are handled. After using toxic materials, trained laboratory personnel should wash their face, hands, neck, and arms. Equipment (including PPE such as gloves) that might be contaminated must never be removed from the environment reserved for handling toxic materials without complete decontamination. Choose laboratory equipment and glassware that are easy to clean and decontaminate. Work surfaces should also be easy to decontaminate or covered with appropriate protective material, which can be properly disposed of when the procedure is complete. Mixtures that contain toxic chemicals or substances of unknown toxicity must never be smelled or tasted. 6. Carefully plan the transportation of very toxic chemicals. Handling these materials outside the specially designated laboratory area should be minimized. When these materials are transported, the transporter should wear the full complement of PPE appropriate to the chemicals and the type of shipping containers being transported. Samples should be carried in unbreakable secondary containment. (See Chapter 5 for more information about transporting laboratory chemicals.) 6.D.6 Preparing for Accidents with and Spills of Substances of High Toxicity Be sure that emergency response procedures cover highly toxic substances. Spill control and appropriate emergency response kits should be nearby, and laboratory personnel should be trained in their proper use. These kits should be marked, contained, and sealed to avoid contamination and to be accessible in an emergency. Essential contents include spill control absorbents, impermeable surface covers (to prevent the spread of contamination while conducting emergency response), warning signs, emergency barriers, first-aid supplies, and antidotes. Before starting experiments, the kit contents should be validated. Safety showers, eyewash units, and fire extinguishers should be readily available nearby. Self-contained impermeable suits, a self-contained breathing apparatus, and cartridge respirators may also be appropriate for spill response preparedness, depending on the physical properties and toxicity of the materials being used (see section 6.C.2.4). Experiments conducted with highly toxic chemicals should be carried out in work areas designed to contain accidental releases (see also section 6.D.3). Trays and other types of secondary containment should be used to contain inadvertent spills. Careful technique must be observed to minimize the potential for spills and releases. Prior to work, all toxicity and emergency response information should be posted outside the immediate area to ensure accessibility in emergencies. All laboratory personnel who could potentially be exposed must be properly trained on the appropriate response in the event of an emergency. Conducting occasional emergency response drills is always a good idea. Such dry runs may involve medical personnel as well as emergency cleanup crews. (See also sections 6.C.10.5 and 6.C.10.6.) 6.D.7 Storage and Waste Disposal Use unbreakable secondary containment for the storage of highly toxic chemicals. If the materials are volatile (or could react with moisture or air to form volatile toxic compounds), containers should be in a ventilated

storage area. All containers of highly toxic chemicals should be clearly labeled with chemical composition, known hazards, and warnings for handling. Chemicals that can combine to make highly toxic materials (e.g., acids and inorganic cyanides, which can generate hydrogen cyanide) should not be stored in the same secondary containment. A list of highly toxic compounds, their locations, and contingency plans for dealing with spills should be displayed prominently at any storage facility. Highly toxic chemicals that have a limited shelf life need to be tracked and monitored for deterioration in the storage facility. Those that require refrigeration should be stored in a ventilated refrigeration facility. Procedures for disposal of highly toxic materials should be established before experiments begin, preferably before the chemicals are ordered. The procedures should address methods for decontamination of all laboratory equipment that comes into contact with highly toxic chemicals. Waste should be accumulated in clearly labeled impervious containers that are stored in unbreakable secondary containment. Volatile or reactive waste must always be covered to minimize release. Follow procedures established by the institution’s EHS experts for commercial waste disposal. Alternatively, consider the possibility of pretreatment of waste either before or during accumulation. In-laboratory destruction may be the safest and most effective way of dealing with waste, but regulatory requirements may affect this decision. (For further information about disposal of hazardous waste, see Chapter 8. For information about regulatory requirements, see Chapter 11.) 6.D.8 Multihazardous Materials Some highly toxic materials present additional hazards because of their flammability (see Chapter 4, section 4.D.1, and Chapter 6, section 6.F), volatility (see sections 6.F and 6.G.6), explosivity (see Chapter 4, section 4.D.3; see also section 6.G.4), or reactivity (see Chapter 4, section 4.D.2; see also section 6.G.2). These materials warrant special attention to ensure that risks are minimized and that plans to deal effectively with all potential hazards and emergency response are implemented. (Table 5.1 provides information regarding incompatible chemicals and substances requiring extreme caution.)

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