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CHAPTER 3: CHEMICAL CLASSIFICATIONS AND USE GUIDELINES

3.1 CLASSIFICATION OF HAZARDOUS CHEMICALS

3.1.1 Health Hazard

Chemicals that are referred to as health hazards are substances for which there is statistically significant evidence, based on at least one study conducted in accordance with established scientific principles, that acute (short term) or chronic (long term or possibly delayed) health effects may occur in exposed individuals. Health hazards include:

Allergens/Sensitizers are substances which may produce skin or lung hypersensitivity. Some common examples of such substances are chromium metal and chromium-containing compounds, diazomethane, nickel metal and nickel- containing compounds, dichromates, formaldehyde, isocyanates and certain phenols.

Please see section 3.2.1 for more specific allergen/sensitizer use guidelines

Carcinogens are substances that promote or initiate the development of malignant or benign growths in living tissue. Carcinogens can be listed as known carcinogens or suspected or potential carcinogens. Some examples of known carcinogens are asbestos, benzene, formaldehyde, inorganic arsenic, chromium and nickel compounds.

Please see section 3.2.9 for more specific carcinogen use guidelines.

Corrosives are substances which visibly erode or irreversibly alter living tissue, and are particularly damaging to the eyes. Respiratory damage, by means of severe bronchial irritation, occurs from the inhalation of the vapors or mists of these types of chemicals. There are three general categories:

  • Strong acids, which generally include nitric, hydrochloric, sulfuric and phosphoric.
  • Strong bases, commonly including ammonia, potassium hydroxide and sodium hydroxide.
  • Dehydrating agents, such as concentrated sulfuric acid, sodium hydroxide, phosphorus pentoxide and calcium oxide.

Please see section 3.2.4 for more specific corrosive use guidelines.

Irritants are substances which cause reversible inflammation of living tissue. Chemicals such as ferrous ammonium sulfate, calcium oxide, sodium chloride, menthol and magnesium hydroxide are considered to be irritants. Please see section 3.2.1 for more specific irritant use guidelines.

Reproductive Toxins are substances which exhibit harmful effects in either the male or female reproductive system, or on the developing fetus. Reproductive toxins can be further subdivided into the following classes:

  • Embryotoxins--substances which are poisonous to the embryo without necessarily being poisonous to the mother.
  • Mutagens--substances which induce changes in DNA and living cells.
  • Terotagens--substances which cause physical or functional defects in the developing embryo. The direct results of teratogenic chemicals are compromised survivability or birth defects in the newborn.

Examples of common reproductive toxins include formamide, lead compounds, ionizing radiation, organomercurials, and the formerly used sedative, thalidomide. Please see section 3.2.9 for more specific reproduction toxin use guidelines.

Target Organ Substances are chemicals which exert a toxic effect on one or more of the various organs or systems of the human body. Target organ classifications include:

  • Hepatotoxins--chemicals which produce liver damage.
  • Nephrotoxins--chemicals which produce kidney damage.
  • Neurotoxins--chemicals which produce toxic effects on the nervous system.
  • Cutaneous hazards--chemicals which affect the dermal layer of the body.
  • Eye hazards--chemicals which affect the eye or visual capacity.
  • Agents which act on the blood or hematopoietic system by decreasing hemoglobin function and therefore deprive the body tissues of oxygen.
  • Agents which damage the lungs by irritating or damaging the pulmonary tissues.

Acute or Chronic Toxins/Poisons--a substance is toxic because of its ability to damage or interfere with the metabolism of living tissue.

  • Acutely toxic substances inflict their damage as a result of a single exposure or an exposure of a short duration. According to the Minnesota Pollution Control Agency (MPCA), the following values define an acutely toxic substance:
  • Oral LD50 (rat) of less than 50 mg/kg
  • Inhalation LC50 (rat) of less than 2 mg/l
  • Dermal LD50 (rabbit) of less than 200 mg/kg

Some examples of acutely toxic substances are hydrofluoric acid, hydrogen cyanide, hydrogen sulfide and nitrogen dioxide. For additional information on acutely toxic chemicals see section 3.2.9.

  • Chronically toxic substances cause damage after repeated exposures or lower dose exposures of a longer duration. Also associated with some chronic toxins are long latency periods in which the cumulative effects of the substance are not evident for many years. Some examples of chronically toxic substances are all carcinogens and many metals and their derivatives (i.e. arsenic, cadmium, lead, mercury and nickel)

All new and untested chemicals should be treated as toxic until scientific evidence proves otherwise. Please see section 3.2.9 for more specific toxin use guidelines.

3.1.2 Physical Hazards

Physical hazards include the following classes:

Combustible Substances are liquids with a flash point of more than 100 °F or solids that are difficult to ignite and that burn relatively slowly. (See section 3.2.5 for the definition of flash point.) Examples of combustible liquids include diesel oil and corn oil.

Compressed Gases are either gases or mixtures of gases in containers having an absolute pressure exceeding 40 pounds per square inch (psi) at 70 °F (21 °C); or a mixture of gases, in a container with an absolute pressure above 104 psi at 130 °F (54.5 °C), regardless of the pressure at 70 °F (21 °C). Compressed gases also include flammable liquids having a vapor pressure greater than 40 psi at 100 °F (37.8 °C).

Please see sections 3.2.2 and 3.2.3 for more specific compressed gas use guidelines.

Explosives are substances that cause a sudden, almost instantaneous release of energy, pressure, gas and heat when subjected to sudden shock, pressure or high temperature. Explosives are separated into classes that range from severe to minimum hazard. Some examples of severe explosives are benzoyl peroxide, dry picric acid and lead azide. Please see section 3.2.7 for more specific explosive substance use guidelines.

Flammable Substances are substances with a flash point of less than 100 °F that readily catch fire and burn in air. A flammable liquid, itself, does not burn--it is the vapors given off from the liquid that do. Different liquids produce flammable vapors at different rates, with the rate dependent on the liquid’s vapor pressure. Common flammable liquids found in laboratories are ethanol, methanol, acetone, ether and toluene. Please see section 3.2.5 for more specific flammable chemical use guidelines.

Oxidizers are substances, other than blasting agents or explosives, that initiate or promote combustion in other materials, causing fire either of itself or through the release of oxygen or other flammable gases. Common oxidizer chemical families include bromates, chlorates, chromates, iodates, nitrates, nitrites, perborates, percarbonates, perchlorates, periodates, permanganates, perioxides and persulfates. Please see section 3.2.7 for more specific oxidizer use guidelines.

Pyrophoric Substances are liquids or solids that will ignite spontaneously in air below 130 °F (54.4 °C). These materials must be stored in an atmosphere of inert gas or under kerosene. White phosphorus and titanium dichloride are pyrophoric.

Water-Reactive Substances are substances that react with water to release a gas which is either flammable or a health hazard. Sodium metal and many of the metal hydrides are water-reactive.

3.2 CHEMICAL USE GUIDELINES

3.2.1 Allergens, Irritants and Sensitizers

Irritants are chemicals which are not corrosive but cause reversible inflammatory effects on living tissues at the site of contact. Sensitizers cause allergic reactions in normal tissue after repeated exposure. When working with irritants and sensitizers:

  • Keep contact to a minimum.
  • Consult and follow the recommendations contained in the appropriate MSDS for specific precautions.
  • Wear appropriate gloves and/or a dust mask as recommended by the manufacturer.

3.2.2 Compressed Gases

Compressed gases include liquefied petroleum gases and oxygen, nitrogen, anhydrous ammonia, acetylene, nitrous oxide, and fluorocarbon gases. When working with compressed gases:

  • Securely fasten compressed gas cylinders in an upright position and in such a manner that they cannot be tipped.
  • Do not expose cylinders to temperatures higher than about 50 °C (122 °F). Some rupture devices on cylinders will release at about 65 °C (149 °F). Small cylinders, such as lecture bottles, are not usually fitted with rupture devices and may explode if exposed to high temperatures.
  • Never lubricate, modify, force or tamper with cylinder valves. The specificity of a regulator fitting must be honored as determined by the Compressed Gas Association.
  • Do not use Teflon tape with regulators.
  • Use a soap solution to test all the connections for leaks before use.
  • Check the MSDS or other sources for safety procedures for the gas being used.
  • Maintain labels. The cylinder decal or label is the only positive way to identify the gas contained within a cylinder. Color codes are not uniform among the manufacturers.
  • Do not smoke or use open flames where oxidant or flammable gases are stored.
  • Cylinders without regulators must be capped and secured at all times.
  • Store all gas cylinders in a well-protected, well-ventilated and dry location, away from elevators, stairs or public hallways.
  • Do not store gas cylinders in unventilated enclosures such as lockers and cupboards.
  • Flammable gas cylinders stored inside buildings must be stored 20 feet away from flammable liquids, highly combustible materials, and oxidizers and not near arcing electrical equipment, open flame or other sources of ignition.
  • Oxidizing gases must be separated by a distance of 20 feet or a non-combustible barrier of at least five feet high (with fire resistance rating of at least one half hour) from flammable gas containers or combustible materials (especially oil or grease).

To move a compressed gas cylinder:

  1. Remove the regulator and replace the protective cap.
  2. Never lift gas cylinders by using the container cap or magnets.
  3. Use a hand truck. Properly secure the cylinder on the truck before beginning the move.
  4. Never drag or slide cylinders, even over short distances.
  5. Avoid subjecting cylinders to excessive mechanical shocks.

When transporting a gas cylinder in an elevator, do not accompany it in the elevator. Instead, use a two-person system for loading and unloading the cylinder from the elevator.

Two references, "Fire Protection for Laboratories Using Chemicals," from the National Fire Protection Agency and "Safe Handling of Compressed Gases in Containers," from the Compressed Gas Association, Inc., are available from the EHSO’s safety reference library.

3.2.3. Toxic Compressed Gases

Extremely toxic gases such as HCN or cyanogen are usually supplied in lecture bottles. (See Chemical List # 23 for IDLH [Immediately Dangerous to Life and Health] and PEL notations.) When working with extremely toxic gases, the following additional precautions are needed:

  • When not in use, store them in a well ventilated area on appropriately sized racks, not just placed on a shelf or stacked.
  • Before use, lecture bottles must be secured in a fume hood.
  • Do not work with a specialty gas unless you are fully familiar with its proper handling procedures and its toxic or corrosive effects.
  • Warn those working nearby in case of a possible leak.
  • When ordering any compressed gas cylinder, make certain the cylinder can be returned to the supplier.

Larger cylinders of extremely toxic gases which cannot fit inside a fume hood should have special provisions of local exhaust and warning systems.

3.2.4 Corrosive Chemicals

Corrosive chemicals cause visible destruction of, or irreversible alterations in, living tissue by chemical action at the site of contact. All of the hydrogen halides, in addition

to being corrosive reagents, have vapors which are serious respiratory irritants. Alkali metal hydroxides and aqueous solutions of ammonia are extremely destructive to both the skin and eye tissues. When working with corrosives:

  • Store liquid corrosives below eye level.
  • Use spill trays under the containers.
  • Never add water to a concentrated acid. Always add acid to water.
  • Refrain from rubbing eyes until fingers are thoroughly decontaminated.
  • Use concentrated corrosive liquids only in the fume hood.
  • Store acids separate from bases and according to compatibility.

Note: Acetic acid is an organic acid and a reducing agent; whereas chromic acid, nitric acid, perchloric acid and potassium permanganate are oxidizing agents and hence are likely to react with acetic acid. Store these acids separately.

Chemical Lists # 2 &13 list common corrosive chemicals.

Corrosive Liquids Dispensing Containers for all Teaching Laboratories

Concentration

Mode of Dispensing

Maximum Container Size

< 3M

Pouring

500 mL

 

Pump-top

1 gallon (4L)

3M — conc.

Pouring

250 mL

 

Pump-top

1 gallon (4L)

Corrosive Liquids Personal Protective Equipment (PPE)

When working with corrosives (i.e. acids, based, amines, etc.) follow these requirements:

 

 

Dispensed

 

Poured

Conc

Volume

PPE

Conc

Volume

PPE

3 M

 

any

goggles

< 3 M

any

goggles

 

up to 25 mL

goggles

 

5 mL

goggles

3–6 M

> 25 mL

goggles, gloves & faceshield*

3–6 M

> 5–25 mL

goggles & gloves

 

 

 

 

> 25 mL

goggles, gloves

& faceshield*

7 M conc.

5 mL

goggles

7 M conc.

5 mL

goggles & gloves

 

> 5–25 mL

goggles & gloves

 

> 5–25 mL

goggles & gloves

& faceshield*

 

> 25 mL

goggles, gloves,

apron & faceshield*

 

> 25 mL

goggles, gloves,

apron & faceshield*

*A fume hood sash, when properly lowered and used, can be substituted for a face shield.

3.2.5 Flammable Chemicals

Flammable chemicals are classified as having a flash point of less than 100 °F. An understanding of the following terms is helpful when working with flammable chemicals:

• Flash point--the lowest temperature at which the vapor above the liquid will ignite if an ignition source is present. The flash point for ethyl ether is - 49 °F.

• Ignition/Autoignition temperature--the minimum temperature required to initiate or cause self-sustained combustion which is independent of a spark or flame source.

• Limits of flammability--each flammable gas and liquid (in the form of a vapor) has two limits which define the range of concentrations in mixtures with air that will propagate flame and explode.

•• LFL or Lower flammable limit--the percent by volume

concentration below which the mixture is too lean to burn.

•• UFL or Upper flammable limit--the percent by volume

concentration below which the mixture is too rich to burn.

•• The flammable range consists of all the concentrations between these two limits.

• Spontaneous combustion or ignition--this phenomenon takes place when, without the application of an external heat source, a substance reaches its ignition temperature.

  • When working with flammable chemicals:
  • Keep in covered containers when not actually in use.
  • Keep all sources of ignition, high heat and combustion remote from storage and dispensing areas. Always keep most organic solvents away from inadvertent contact with oxidizers.
  • Dispense all solvents within a fume hood.
  • Do not use Nalgene carboys for storage of flammable liquids. Follow the flammable liquid container size limits found in Appendix 11.
  • Do not store flammable liquids on the floor.
  • Store and use in the smallest amounts possible so that any spill can be cleaned up before it can cause a large fire.

Chemical Lists # 3, 4, 17 & 18 list common flammable chemicals.

Static Electricity, Bonding and Grounding

Static electricity is generated by the contact and separation of dissimilar materials. For example, static electricity is generated when a fluid flows from a container opening down a funnel, through agitation and mixing and through filling a container which causes splashing. In the case of flammable liquids, spark discharges from the static electricity build-up may have enough energy to ignite the flammable vapors present. In order to prevent these discharges by providing a good electrical-conductive path, proper bonding and grounding procedures of the equipment involved must be carried out.

By definition, bonding is a procedure which eliminates static-electrical-charge differences between two or more objects. Grounding, on the other hand, is a procedure which eliminates a potential difference between an object and the ground (earth).

When two objects are bonded, the charges flow freely between the objects and there is no difference in their charge. Bonding will not eliminate the static charge but will equalize the potential between the objects bonded so that a spark will not occur between them. Bonding will eliminate a difference in potential between objects that are bonded. However, it will not eliminate a difference in potential between these objects and the earth, unless one of the objects has an adequate conductive path to earth. An adequate ground, which will continuously discharge a charged conductive body, is necessary to complete the conductive path.

Bonding and grounding are only effective when the bonded objects are made of conductive materials. Plastics can accumulate significant static electrical charge without

allowing the charge to disperse enough through the material. Therefore, non-approved

plastic containers and funnels should not be used when transferring flammable liquids in quantities larger than one gallon.

The equipment necessary to carry out bonding and grounding is available in the stockroom.

Bonding and Grounding Procedures for transferring flammable liquids in quantities greater than one gallon:

Please note that only metal funnels and the appropriate containers, preferably plastic safety cans, should be used. Please see Appendix 11 for flammable liquids container

requirements. Whenever possible, perform the transfer in a fume hood.

1.  Using a bonding/grounding wire, connect the original container to the funnel. Using another wire, connect the funnel to the receiving container. If the containers involved are metal and coated in some way (paint, plastic), scrape down to the metal with the clamp on the wire to ensure a good connection.

2. Using a bonding/grounding wire, connect the container to a ground source such as the water spigot in the hood or another conductive metal source. Ensure good connections.

3. Perform the transfer.

3.2.6 INFECTIOUS AGENTS

Academic Use

Proper laboratory procedures to follow when working with infectious or potentially infectious agents are not within the scope of this CHP. Prudent practices to follow when working with these agents are contained in reference texts such as the Centers for Disease Control and National Institute of Health’s "Biosafety in Microbiological and Biomedical Laboratories"--NIH No. 88-8395 and the National Research Council’s "Biosafety in the Laboratory" available through the Environmental Health and Safety Officer’s reference library.

Additionally, the CSB and SJU bloodborne pathogens written policy, as required by 29 CFR 1910.1030, are available through the safety offices of each campus. Under these policies laboratory work involving human blood or other potentially infectious materials must be reviewed by the Environmental Health and Safety Officer before any work commences.

Potential Exposure Incidents

All faculty, staff, student employees and students must take steps to lessen the chance of exposure to human blood and other potentially infectious materials. Gloves must beworn whenever the potential for contact with an open wound exists. Bloodborne Pathogen Supply kits, which contain gloves and all of the supplies necessary to clean-up areas contaminated by potentially infectious materials, are available in the stockroom and rooms 213, 237 and 238.

Please see Chapter 4 for more information on emergency response. Additionally, theCSB and SJU bloodborne pathogens policies contain more information on related issues.

3.2.7 Explosives, Highly Reactive Chemicals and Oxidizers

Unstable or reactive chemicals are those which in the pure state or as commercially produced, will vigorously polymerize, decompose, condense or will become self-reactive under conditions of shock, pressure or temperature. Compounds containing the following functional groups tend to be sensitive to heat and shock: acetylide, diazo, nitroso, peroxide, azide, halamine, ozonide.

Compounds containing nitro groups may be highly reactive, especially if other substituents such as halogens are present. Treat the following groups with respect, especially at higher temperatures: perchlorates, nitrates, chlorites, chlorates, bromates, iodates. Highly reactive chemicals may be included on the list of chemicals requiring prior approval. Please consult those guidelines before use. (Section 2.7 and Appendix 4)

Special handling procedures for highly reactive chemicals:

Consult guidelines in the appropriate references or MSDSs before using chemicals exhibiting these properties.

  • Research advisors are responsible for informing their research students of the hazards associated with working with highly reactive chemicals before any work commences.
  • Bring these chemicals into the laboratory only as required and then in the smallest possible quantities.
  • Do not mix even small quantities with other chemicals without prior knowledge of the hazards involved.
  • Wear safety goggles, a lab coat, appropriate gloves and use an explosion shield.
  • Highly reactive chemicals cannot be stored in the same room as flammable liquids. Please see the stockroom manager for the designated storage location.

Lists of common reactive and explosive chemicals are included as Chemical List # 10, 11, 14, 15 & 16. Additionally, lists of common oxidizers and oxidizer chemical families are included as Chemical Lists # 6 & 7.

3.2.8 Radioactive Chemicals

Radioactive materials will not be used in Ardolf Science Center.

3.2.9 REPRODUCTIVE TOXINS, SELECT CARCINOGENS and ACUTE and CHRONIC TOXINS (PARTICULARLY HAZARDOUS SUBSTANCES)

Toxicity

Parameters for judging the toxicity of a chemical include the following terms:

• Lethal Dose (LD50) is the quantity of material that when ingested, injected or applied to the skin as a single dose will case the death of 50% of the test animals.

• Permissible Exposure Limits (PELs) are OSHA-regulated values which define the legal air contaminant concentrations in the workplace. PELs are expressed in ppm (parts of vapor or gas per million parts of air by volume at room temperature and atmospheric pressure) or mg/m3 (milligrams of particulate per cubic meter of air).

• Threshold Limit Values (TLVs) refer to airborne concentrations of substances and represent conditions under which it is believed that nearly all workers may be repeatedly exposed day after day without adverse health effects. TLVs can be further broken down into:

Time-Weighted Average (TLV-TWA) is the time-weighted average concentration for a normal 8-hour workday and a 40-hour workweek.

Short-Term Exposure Limit (TLV-STEL) is the concentration to which persons can be exposed for a period of up to 15 minutes continuously without suffering irritation, chronic or irreversibly tissue change or narcoses.

TLV have been determined by the American Conference of Governmental Industrial Hygienists, ACGIH.

In general the lower the LD50, PEL or TLV, the more hazardous the material.

Chemical List # 23 is the University of Minnesota list of regulated chemicals, with their PELs and TLVs. The U of M list also includes notations of MREP (male reproductive toxin), FREP (female reproductive toxin) and DTOX (developmental toxin). Additionally, the following common lists, compiled from 33 State and Federal Regulatory Lists, are found in the Chemical List section :

Chemical List # Chemical Group

1 & 12 Carcinogens

19 Extreme Acute Health Ratings

20 Extreme Chronic Health Ratings

21 Neurotoxins

1 & 22 Teratogens

Carcinogens

According to Hawley’s Condensed Chemical Dictionary, 11th Edition, there are approximately 3500 known and suspected carcinogenic compounds, with new compounds being discovered continually. The following groups publish lists of carcinogenic substances:

  • National Toxicology Program as "known to be carcinogenic" or "reasonably anticipated to be carcinogens" in the latest edition of the Annual Report on Carcinogens.
  • Occupational Safety and Health Administration (OSHA) regulated as such in 29 CFR 1910.1000, Subpart Z.
  • International Agency for Research on Cancer (IARC) as Group 2A or 2B in the latest edition of Monographs.

Please see the University of Minnesota list of regulated chemicals, Chemical List # 23, columns P, Q and R for more specific information.

Safety Guidelines:

A minimum set of guidelines that should be followed when working with reproductive toxins, carcinogens, acutely toxic chemicals and experimental chemicals with unknown toxicity are listed below. The Lab Coordinator or Research Advisor should ensure that these and other necessary precautions are taken when working with these substances.

  • Use of these chemicals must be approved by the Lab Coordinator or Research Advisor before beginning any reaction, manipulation or operation. Please note that some of these chemicals may also require prior approval or notification before use. See Appendix 4 for guidelines.
  • All work must be performed in a functioning fume hood, biological safety cabinet, ventilated glove box, sealed system or other system designed to minimize exposure to these substances.
  • Gloves and other appropriate protective apparel must be worn when working with these chemicals. Check the chemical’s MSDS for the appropriate personal protective equipment.
  • The quantities used and stored in the laboratory and their concentrations in solution or mixtures must be minimized.
  • Decontaminate and clean the work area at appropriate intervals. Follow a procedure approved by the Lab Coordinator in consultation with the Environmental Health and Safety Officer. The interval may be as short as one day or as long as six months depending upon the frequency of usage and level of hazard.
  • All contaminated wastes must be collected and disposed of in a timely and appropriate manner as outlined in the CSB/SJU CHP. For more specific disposal information contact the Environmental Health and Safety Officer.
  • When not in use, these chemicals should be stored in a limited access area and within protective containment devices.
  • Volatile substances should be kept cool and contained.
  • Dispersible solids should be kept in closed containers, used in places with minimum air currents, and suitable contact materials should be used to avoid static charge buildup.
  • Compressed gas cylinders which contain acutely toxic chemicals such as arsine and nitrogen dioxide must be kept in ventilated gas cabinets.
  • Ensure control of gases by using piping, valves and containers which can withstand pressure buildup.
  • Detection equipment may be required in laboratories where chemicals (especially poisonous gases) with a high degree of acute toxicity are utilized.
  • Anyone whose work involves regular and frequent handling of toxicologically significant quantities of a chemical should consult with the Environmental Health and Safety Officer to arrange for a qualified physician to determine whether a regular schedule of medical surveillance is desirable.
  • Employees must comply with the recommendations contained in the National Institutes of Health (NIH) publication entitled "NIH Guidelines for the Laboratory Use of Chemical Carcinogens," which is available through the Environmental Health and Safety Officer’s safety reference library.