Hazardous Materials Releases
Hazardous materials releases (i.e., spills) will occur at any time anywhere on campus, especially in laboratories and facilities and maintenance areas. All people who work within those areas should be instructed how to prepare for and what to do in case of a spill, fire or other emergency.
Prepare for a Spill
Assess your area. Determine what chemicals are present and the hazard of each. Plan for a spill of the largest container of each chemical type. Determine if you have chemicals which will require specialized cleanup equipment and procedures (e.g., mercury, hydrofluoric acid, bromine, etc.). Keep Safety Data Sheets (SDS) for all chemicals in a centralized location. Post emergency contact information and evacuation routes. Know where equipment shutoff switches are located. Know the location of the nearest eyewash, safety shower, fire pull and type and location of fire extinguisher. the outside of the building. Establish procedures for responses to personal injuries.
Assemble a spill kit. The general requirement is to protect yourself while you absorb and/or neutralize the spilled material and then clean the spill. Thus, items you may need in a spill response kit include:
Personal protective equipment
- 2 pair of chemical splash goggles
- 2 pair of gloves (e.g., Silver shield, Nitrile, etc., a universal glove)
- 2 pair of shoe covers
- 2 plastic or Tyvek aprons and/or Tyvek suits
- Absorbent pillows / powders (e.g., 3M Powersorb or other commercial products)
- Activated carbon (good for organic solvents)
- Floor-dry / Oil-dry (inexpensive absorbent)
Neutralizing materials (Consider special materials: HF, Hg, Br, etc.)
- Acid neutralizer
- Caustic neutralizer (e.g., Neutrasorb [for acids] and Neutracit-2 [for bases](include a color change substance to indicate complete neutralization)
- Solvent neutralizer (e.g., solusorb, activated carbon) to reduce vapors and raise the flash point of the mixture
- Polypropylene scoop or dust pan
- Broom or brush with polypropylene bristles
- 2 five (5) gallon polypropylene pails
- 2 polypropylene bags
- Sealing tape
- pH test papers
- Sign: Danger Chemical Spill – Keep Away
Train all personnel. Instructors,Principal Investigators and Supervisors should ensure that everyone under their supervision receives appropriate and adequate information and training to be able to respond safely to a hazardous materials spill or release within their area. The level and content of training required and the level of response permitted will vary by individual/position and will be dictated by institutional policy.
Assess the Spill
There are many terms that distinguish spills that can be managed easily (minor, simple, small, incidental, etc.) from those that require outside help (major, complex, emergency, etc.). Simplistically, a minor spill is a spill that can be managed by the person who spilled the material and a major spill is a spill that exceeds those capabilities. To help distinguish a major from minor spill, a decision tree or similar tool should be included in the university Emergency Response Plan, Emergency Action Plan and the Chemical Hygiene Plan. A sample is below:
An incidental release is a release of a hazardous substance which does not pose a significant safety or health hazard to employees in the immediate vicinity or to the employee cleaning it up, nor does it have the potential to become an emergency within a short time frame. Incidental releases are limited in quantity, exposure potential, or toxicity and present minor safety or health hazards to employees in the immediate work area or those assigned to clean them up. An incidental spill may be safely cleaned up by employees who are familiar with the hazards of the chemicals with which they are working.
The properties of hazardous substances, such as toxicity, volatility, flammability, explosiveness, corrosiveness, etc., as well as the particular circumstances of the release itself, such as quantity, confined space considerations, ventilation, etc., will have an impact on what employees can handle safely and what procedures should be followed. Additionally, there are other factors that may mitigate the hazards associated with a release and its remediation, such as the knowledge of the employee in the immediate work area, the response and personal protective equipment (PPE) at hand, and the pre-established standard operating procedures for responding to releases of hazardous substances. There are some engineering control measures that will mitigate the release that employees can activate to assist them in controlling and stopping the release.
These considerations (properties of the hazardous substance, the circumstances of the release, and the mitigating factors in the work area) combine to define the distinction between incidental releases and releases that require an emergency response. The distinction is facility-specific and is a function of the emergency response plan.
Reference Interpretation and Compliance Letters:
- Emergency situations that fall under Hazwoper.[11/8/91]
- Considerations for “incidental” spills cleaned up by maintenance personnel to satisfy the definition of “emergency response.”[7/31/90]
See Also: OSHA Instruction CPL 2-2.59A, Appendix E, Inspection Procedures for the Hazardous Waste Operations and Emergency Response Standard, 29 CFR 1910.120 and 1926.65, Paragraph (q): Emergency Response to Hazardous Substance Releases [04/24/98]
Clean the Spill
General guide for chemical spills:
- Isolate the spill area; alert others
- Determine identity of spill material; consult MSDS to determine potential hazards
- Avoid breathing vapors, get as much fresh air into area as you can safely
- Establish ventilation to the outside if safe; prevent the contaminant from spreading through building
- Absorbents and neutralizing agents must be compatible with chemical spilled
- Prevent spilled chemicals from going down drains to avoid affecting the environment
- Dispose of cleanup materials as chemical hazardous waste; small volumes of dilute acids and bases may be neutralized (pH 6-8) and sewered
- Call EHS for hazardous waste pickup or for guidance on cleanup or air monitoring
Simple spills: liquid
- Alert people in area
- Wear protective equipment
- Contain by diking with appropriate absorbent
- Flammable–remove ignition sources (burners, motors, anything that could cause a spark); use plastic or nonmetallic cleanup equipment
- Absorb or neutralize with appropriate agent working from outside edges inward; sorbents do not remove toxic or flammable hazards; neutralization can produce heat causing boiling and splattering
- Acid—use sodium bicarbonate or acid spill kit
- Base—use sodium bisulfate, citric acid, or base spill kit
- Formaldehyde–absorb or use polymerize
Simple spills: dry
- If not water reactive, dampen to prevent airborne dust
- Control water reactive dust with sweeping compound
- Carefully brush solids into a dust pan or container
- Keep dust generation down to prevent creating inhalation hazard
Compressed gas leak–simple
- Presents no or only minimal inhalation or fire hazard
- Remove ignition sources
- Restrict access
- Place in or next to fume hood if possible; tighten fittings
- Locate leak with soapy water (at below freezing temperatures use 50% glycerine solution)
- If cylinder still leaks, contact supplier
- Notify your supervisor
Compressed gas leak–major
Large or uncontrollable leak or fire hazard, involves acutely toxic gas, and/or more than minimal personal risk
- Alert others to evacuate
- Call 911
- Turn off ignition sources
- Leave fume hoods running; ventilate the affected area prior to leaving the area (only if it can be done safely and only to the outside)
- Evacuate; assemble in a remote location; account for people
- Provide information to emergency responders
- Notify your supervisor
SPILLS REQUIRING SPECIAL PROCEDURES
- Use Oil-Dri, Zorb-All, or dry sand.
- Avoid water and avoid sodium bicarbonate.
Alkali Metals (lithium, sodium, magnesium, potassium)
- Smother with dry sand or cover with contents from a Class “D” fire extinguisher. Use of a Class “D” fire extinguisher is the preferred extinguishing method.
- Avoid contact with water.
White or Yellow Phosphorus
- Blanket with wet sand or wet absorbent.
- Neutralize spill with a 5% solution of sodium thiosulfate.
- Absorb with inert absorbent material.
*See special emergency treatment below
- Neutralize with soda ash or lime (or absorb spill with special HF spill pillow).
- Absorb with inert absorbent material.
- Use aspirator bulb or suction device to collect mercury beads (Do not use a vacuum
- Mop up mercury with mercury decontaminating powder.
SPECIAL EMERGENCY TREATMENT
Hydrofluoric Acid Contamination
1. Immediately flush with copious amounts of water under an emergency shower.
2. Remove all clothing while under the shower. Flush skin for 5 minutes.
3. Apply calcium gluconate gel (2.5%) while wearing clean impervious gloves. (If calcium gluconate gel is not available continue to flush skin until medical personnel arrive).
4. Get medical attention immediately.
1. Immediately flush eyes with water under an eyewash for 15 minutes.
2. Get medical attention immediately.
1. Remove victim to fresh air.
2. Get medical attention immediately.
Inform medical personnel that injury involves hydrofluoric acid and give them a copy of the material safety data sheet.
The spill law, Chapter 292.11, Wis. Stats., requires that a person who possesses or controls a hazardous substance or who causes the discharge of a hazardous substance shall notify the department immediately of any discharge not exempted by the statute. The Department has a 24-hour toll free number for reporting spills: 1-800-943-0003.
In order to determine whether you have a hazardous substance spill that requires immediate notification, you must ask yourself the following three questions: 1) Is the substance spilled a hazardous substance; 2) Has it been released to the environment; and 3) Are there statutory or rule exemptions that apply to this situation. The following text should help you answer those questions, and provides you with insights into unusual spills that did require notification.
Chapter 292.01(5), Wis. Stats., defines a hazardous substance as “any substance or combination of substances including any waste of a solid, semisolid, liquid or gaseous form which may cause or significantly contribute to an increase in mortality or an increase in serious irreversible or incapacitating reversible illnesses or which may pose a substantial present or potential hazard to human health or the environment because of its quantity, concentration or physical, chemical or infectious characteristics. This term includes, but is not limited to, substances which are toxic, corrosive, flammable, irritants, strong sensitizers or explosives as determined by the department.” The rule of thumb used by many is if you have to think about whether it needs to be reported, it probably does. Remember, reporting spills never gets you into trouble, only failure to report does. A hazardous substance that is released into a secondary containment structure, completely contained and can be recovered with no discharge to the environment, is not “discharged” as that term is used in s. 292.11, Wis. Stats. Only discharges to the environment require notification to the DNR.
If you’re not sure whether you have a spill that needs to be reported, call the 24-hour toll free hotline, 1-800-943-0003, and you will be provided with guidance on reporting. In many situations, spill report forms are not completed if the incident is not considered a hazardous substance spill to the environment. You will need to provide information such as your name, address, location of the discharge; physical state, quantity, chemical characteristics of the discharged substance; cause of the discharge; destination of the discharged substance; actions taken to stop the release/minimize the impact to the environment actual or potential impacts to human health or the environment
De Minimus Exemptions:
Wisconsin Administrative Code establishes exemptions for small quantity spills of agricultural and petroleum related compounds, as well as substances that have a federal reportable quantity established. These quantities are termed “de minimis” in that below these levels, under the following conditions, state notification of a discharge is not required. While reporting requirements may be exempted, cleanup requirements remain.
De Minimus Exemptions are as follows:
Discharges of Petroleum compounds if you spill:
- gasoline or another petroleum product is completely contained on an impervious surface.
- less than one gallon of gasoline on a pervious surface or runs off an impervious surface.
- less than five gallons of other petroleum products on a pervious surface or runs off an impervious surface.
Discharges of Agrichemical compounds if:
- the amount is less than 250 pounds of a dry fertilizer.
- the amount is less than 25 gallons of a liquid fertilizer.
- the amount discharged when diluted as indicated on the pesticide label would cover less than one acre of land if applied according to label instructions for pesticides registered for use in Wisconsin.
Federal reportable quantities: if the amount discharged is less than the federal reportable quantity.
The DNR Spills Web Page is here: http://dnr.wi.gov/topic/Spills/
Federal Reporting Requirements
Spills that exceed a federal reportable quantity must also be reported to the National Response Center, (800) 424-8802, Wisconsin Emergency Management, your Local Emergency Planning Committee and possibly EPA Region 5.
Contact information for your Local Emergency Planning Committee should be in your facility contingency plan (LQG), your campus emergency response plan and your campus emergency action plan. A list of County Emergency Contacts can be found here.
Reporting a hazardous substance release or oil spill takes only a few minutes. To report a release or spill, contact the federal government’s centralized reporting center, the National Response Center (NRC) at 1-800-424-8802. The NRC is staffed 24 hours a day by U.S. Coast Guard personnel, who will ask you to provide as much information about the incident as possible. If possible, you should be ready to report the following:
- Your name, location, organization, and telephone number
- Name and address of the party responsible for the incident
- Date and time of the incident
- Location of the incident
- Source and cause of the release or spill
- Types of material(s) released or spilled
- Quantity of materials released or spilled
- Medium (e.g. land, water) affected by release or spill
- Danger or threat posed by the release or spill
- Number and types of injuries or fatalities (if any)
- Weather conditions at the incident location
- Name of the carrier or vessel, the railcar/truck number, or other identifying information
- Whether an evacuation has occurred
- Other agencies notified or about to be notified
- Any other information that may help emergency personnel respond to the incident
If reporting directly to the NRC is not possible, reports also can be made to the EPA Regional office or the U.S. Coast Guard Marine Safety Office in the area where the incident occurred. In general, EPA should be contacted if the incident involves a release to inland areas or inland waters, and the U.S. Coast Guard should be contacted for releases to coastal waters, the Great Lakes, ports and harbors, or the Mississippi River. The EPA or U.S. Coast Guard will relay release and spill reports to the NRC promptly.
First responders to major incidents will likely be your local fire department or regional hazardous incident team. Make sure current contact information for those agencies is readily available.
Emergency Spill Response Zone Contract
DNR has established a contract to provide emergency response activities for one or more categories of discharges of materials (All Hazards, Petroleum, and Manure) that impact or threaten to impact human health, safety, welfare, or the environment in various regions throughout the state. University of Wisconsin institutions are eligible to use the contract. You should familiarize yourself with the contract provisions and pre-select responders for your area and incident type.
This publication was prepared for environmental, health and safety staff at University of Wisconsin System campuses, to assist in finding resources and information for regulatory compliance. It is not intended to render legal advice.