Appendix Q - CHEMICAL SPILL RESPONSE PLAN

PURPOSE: What to do with this document

This document (based on recommendations of the American Chemical Society's Taskforce on Lab Waste Management) provides guidelines to faculty and staff for planning for and responding to chemical spills. According to the ACS Task Force:
If handled properly, a spill may be nothing more than a nuisance. If handled improperly, a spill can seriously disrupt your activities and the work of your colleagues. At worst, a spill can cause bodily harm or property damage. [...] Trained hazardous material spill responders have learned that it is much better to be overly cautious in responding to a spill than to risk lives for something that "shouldn't be too dangerous." Do not downplay the seriousness of potentially hazardous spills.

Overview: Three steps in order to be prepared for spills: You should: 1) use the SDS to become familiar with the particular hazards and necessary cleanup procedures for each chemical that you use; 2) identify the Spill Response Procedure below for that chemical type, or if the chemical you are using does not have a written procedure below, use the general guidelines and SDS to think/talk through a procedures that you would follow if there was a spill of that chemical; 3) familiarize yourself and others working in the area with the appropriate Spill Response Procedure (below), and with the spill response equipment (detailed below), and train any staff and students working without direct and continuous supervision of lab faculty and staff, using the SDS and spill response procedures. Here is a little more detail about each of these three steps:

1) KNOW THE CHEMICAL HAZARDS: Before implementing a new laboratory procedure, identify the hazards associated with each chemical substance. Read through the SDS (in the red folders in the north hallway, and also readily available online) for each chemical. While reading, specifically think through precautions that should be taken in using that material (e.g. appropriate PPE), and also what would need to be done if a spill of that material were to occur. Determine the hazard class for each chemical. The chemical properties that are particularly important to consider are the following:

Flammability (e.g. ether, acetone, methanol, ethanol, hexanes, acetonitrile, and xylene)
Reactivity to air or water (e.g acid chlorides, reactive metals, and organometallic compounds)
Corrosivity (e.g. concentrated acids, bases, and oxidizing agents)
Toxicity (e.g. mercury, lead, and other heavy metals, cellular toxins, and DNA stains)

2) FORMULATE OR IDENTIFY SPILL RESPONSE PROCEDURES: There are four written Spill Response Procedures below for four specific chemical/hazard types (flammable liquids, concentrated acids and bases, mercury, and acid chlorides). In our setting where we work with very small volumes of most other chemicals/hazards types (particularly air and water reactive or highly toxic compounds), a discussion of a plan with the affected students and colleagues, and with the CHO, prior to the chemical's use will suffice. Things to think through and discuss include:

Who to alarm
The first aid, shower, eyewash, or emergency call procedures that might be required (if spill is on a person or involves obvious injury)
Evacuation procedures
PPE, safety equipment, and cleanup materials required
Lab safety issues related to spill (electrical and heat sources, incompatible chemicals in area)
Packaging and disposal
Who to inform

Use the general guidelines below to assist you in defining these procedures. The CHO is very happy to help with this exercise in forethought, if needed.
3) TRAINING AND FAMILARIZATION: Get to know the procedure and general guidelines, and train staff and students working with the materials regarding the procedures that should be taken in response to a spill. When a spill occurs, the faculty person or staff member who causes the spill, or was overseeing the lab procedure when a student causes a spill, is responsible for initiating the cleanup process and determining if outside help is required. Training of students for spill response procedures is not only a legal obligation, but an opportunity for training students to work safely in the laboratory, beyond EMU.

EMU spill response general guidelines and specific procedures:

Few laboratory spills at EMU present a significant threat since most of the activities use small volumes and solutions. Preparation of working solutions does involve dealing with larger volumes and higher concentrations, and is typically done in the chemical storeroom, in a fume hood. However, the possibility of a large spill of highly hazardous material in one of the labs is still possible. The size of the spill and the hazard properties of the chemical are used together to determine the best response to the spill.

General Guidelines: In the case of a chemical spill, lab faculty and staff should -
Alert and call for assistance:
1. Immediately alert the person who has responsibility for the area – faculty teaching in the area and/or the Chemical Hygiene Officer – and evacuate the area if you are not prepared to deal with the event.
2. In the event of a fire or obvious injury, dial 9-911 and also contact the Chemical Hygiene Officer 432-4420 (cell: 630-995-1955), the EMU Health Services 432-4308 and the Site Safety Coordinator, 432-4396.
3. Assess the size and hazard of the spill – determine whether the spill merits outside help. Factors that clearly indicate a major spill beyond the capabilities of lab faculty or staff:
  1. Release poses conditions that are known to be dangerous to life and health
  2. Release poses serious threat of fire or explosion (e.g. flammable spill in a lab with an operating heat source)
  3. The laboratory responder is uncertain he/she can handle the severity of the hazard with the PPE, equipment, and training provided
  4. Data is lacking relative to the hazard characteristics of the substance
Attend to contaminated persons:
1. Shower or eyewash: The Chemical Hygiene Officer and the faculty member or staff person are responsible for implementing appropriate decontamination for minor spills without obvious injury, should they occur on a student's body. In the event of skin or eye contact with a chemical that will produce an injury, begin decontamination via the safety shower and/or eye wash and relocate subject to a safe area as soon as possible. If the subject is in an unsafe environment and movement could exacerbate injuries, select the action that will produce the lesser injury.
2. Clothing: The faculty member or staff person is responsible to decide whether the level of chemical hazard dictates whether contaminated clothing must be removed; in the case of concentrated strong acids and bases spilled on the person, clothing should be removed immediately and the skin flushed with water for no less than fifteen minutes.
3. Further decontamination: Upon the arrival of the outside emergency responders they will also "hose down" contaminated subjects prior to transporting them to the local hospital.
Attend to the spill area and cleanup:
1. Cordon off the spill area to prevent inadvertent spreading of the contaminant. Protect floor drains or other means of environmental release. Chemically compatible spill socks or absorbents may be placed around the drains as needed.
2. Re-enter: If the area is to be re-entered, consideration must be given to the selection of personal protective equipment appropriate for the hazard. Consult the SDSs for guidance. The use of a respirator requires specialized training and medical surveillance. Only personnel who have been fitted and trained by the CHO and EMU Health Services within the previous year should use a well-fitted respirator.
3. Compatibility: Consider the possibility that the vapors or liquid will migrate to other areas and come into contact with people or incompatible materials, such as oxidizing agents or electrical equipment. Take steps to minimize such occurrences.
4. Cleanup: Use the spill kits located in each laboratory. Specifics on the use of the cleaning materials for several hazard types are given below.
5. Decontaminate the spill surface by mopping, using a mild detergent and water.
6. Waste: Place the cleanup waste (absorbant material, paper towels, etc…) from a small spill into a quart or gallon size polyethylene bag; put larger amounts into 5 gallon plastic pails with polyethylene liners. Identify the container contents with: its hazard category (flammable, corrosive, toxic) and the words "cleanup debris" and affix a date.
Report:
1. CHO: All students should report all spills to the responsible faculty or staff person. All spills are to be reported to the CHO. The CHO will report spills to EMU health services, EMU Safety Coordinator, and/or to the DEQ and HRSSA, as needed.
2. Health services: In the case of any injury or spill on a person, the event must be reported to the EMU health center director, Irene Kniss, 432-4302, Irene.kniss@emu.edu(CHO will do this reporting). In consultation with the health center director, reporting may need to go on to human resources as well.
3. Department of Environmental Quality Reporting (DEQ): A spill of one pound or more of a hazardous waste requires notifying the local DEQ Office. (The CHO will do this reporting.)
4. Harrisonburg Rockingham Regional Sewer Authority (HRSSA): Spills of any amount of hazardous chemicals into the laboratory drain must be reported to the HRRSA, Environmental & Safety Manager, Anita Riggleman, (540) 434-1053 ext. 227 ariggleman@hrrsa.org The CHO will do this reporting.

SPILL RESPONSE CONTAINERS Each laboratory in the Science Center has a visible, accessible Spill Response Kit consisting of the following items:
All kits are contained in a 5 gallon plastic bucket with screw top lid
PPE: Gloves (nitrile), apron, goggles, shoe covers, barricade tape
General cleanup materials:
1. Squeeze bottle with aspirator cap or eyedropper
2. Plastic 100 ml wide mouth collection bottle for use with aspirator
3. Fine bristle brush
4. Plastic dust pan
5. Pint size plastic Ziploc polypropylene bags, scoop and dust pan
6. Quart size heavy duty plastic bag
7. Heavy duty, poly bags, gallon size
Absorbent materials:
1. Spill pillows
2. Paper towels
3. "Pigs", HazMat pads with acid base neutralizer and indicator
4. Quart container of 'Oil Dri' clay absorbent
Acid/base spill specific materials:
1. Acid neutralizer - 5 lbs, 'Draino' (sodium hydroxide)
2. Base neutralizer- Citric acid – 2, 1 lb
3. pH paper (wide range)
Mercury spill specific materials:
1. Mercury absorbent powder – amalgam powder – reduces concentration of vapors in hard to reach areas.
2. Mercury Indicator powder – detects presence of mercury.

SPILL RESPONSE PROCEDURES: Specific procedures for cleaning up incidental (small) spills

These procedures apply to small spills that can be cleaned-up by laboratory personnel after determining that the adverse effects to personnel health, physical property and the environment are understood and are small. Large spills of more hazardous material must be cleaned up by trained on site personnel or off site emergency responders. Laboratory workers are qualified to clean up spills that are "incidental". OSHA identifies incidental spills as "a spill that does not pose a significant health hazard to employees in the immediate vicinity nor does it have the potential to become an emergency within a short time."

1. Spill response procedure for incidental spills of concentrated acid or base:

Acids and bases are perhaps the most used hazardous materials at EMU. For the most part, in the laboratories we use dilute acids (lower than 3 molar), in relatively small volumes. Thus, the most likely time for acid/base spills is in the preparation of solutions, using large volumes (up to 2 gallons) of highly concentrated acids. Particular care should be taken in this step of any procedure, and special training should be provided to any students who help with this task. When a spill of this type happens, go through these steps:

Can I do this? Use the chart below as a guide to determine the approach for cleaning up a spill of concentrated (>3M) acids or bases. (Any use of hydrofluoric acid should be reported to the CHO prior to purchase, since particular precautions need to be made.)

CATEGORY	SIZE	RESPONSE
SMALL	Up to 500 ml	INORGANIC acids or bases (e.g. HCl, H₂SO₄): Neutralization followed by absorbent ORGANIC acids (e.g. glacial acetic, formic): Use absorbent – (flammable procedure)
LARGE	More than 500 ml	OUTSIDE HELP (call CHO)

Open the spill kit: Acid/Base Spill Kit
1. PPE: Gloves - nitrile, apron, goggles, shoe covers
2. Acid neutralizer Soda ash – 5 lbs, Draino (sodium hydroxide)
3. Base neutralizer- Citric acid – 2, 1 lb
4. Oil Dri ('universal' absorbent)
5. pH paper – wide range
6. "Pigs", HazMat pads with acid base neutralizer and indicator
PPE
Control the spread of the liquid by making a dike around the edge of the spill with absorbent Oil Dri or paper towels
Neutralize spilled inorganic acids (HCl, sulfuric, phosphoric) with Draino, sodium bicarbonate, or calcium carbonate. (Concentrated organic acids such as glacial acetic and formic acids may ignite during neutralization. Use flammable liquids guidelines instead of these.) Neutralize spilled base solutions with citric acid.
Mop or sweep up neutralized material and dispose of it in the trash. Sweep neutralized solid residue onto a plastic dustpan and place it a double plastic Ziploc bag or jar.
Further decontaminate the area by mopping floor with a regular detergent and water.
Acids that may be neutralized are hydrochloric, sulfuric, nitric and phosphoric. Do not neutralize concentrated acid spills that contain heavy metals or organic acids

1. Spill response procedure for mercury spills:

We use relatively little mercury in our laboratories. However, we still do use some, particularly in high temperature thermometers. Mercury spills are thus, mostly likely to occur in the organic chemistry laboratory. Students should be informed of the particular hazards that mercury imposes, and informed to leave the room to allow for prompt and safe cleanup. In the event of a mercury spill:

1. 1. Inform room occupants of the event, evacuate/barricade the area if it is a significant spill (>100 ml)
  2. Open the Mercury Spill Kit (part of the bucket of spill kits)
    1. Squeeze bottle with aspirator cap or eye-dropper.
    2. Plastic 100 ml wide mouth collection bottle for use with aspirator
    3. Mercury absorbent powder – amalgam powder – reduces concentration of vapors in hard to reach areas.
    4. Mercury Indicator powder – detects presence of mercury.
    5. PPE: Nitrile gloves, shoe covers
    6. Pint size plastic Ziploc polypropylene bags, scoop and dust pan
    7. Paper towels
    8. Barricade tape
  3. PPE: Don shoe covers, lab coat, and gloves before entering contaminated area.
  4. Collect: Use squeeze bottle to collect the pool and droplets.
  5. Amalgamate: Cover the spill area with a fine dusting of amalgamate, cover amalgamate with a single layer of a paper towel; generously dampen the towels with water. Allow 15 – 20 minutes for amalgamate to react with the mercury.
  6. Cleanup: Use the damp paper towels or a damp amalgam impregnated sponge to pool and remove the residue and place the residue into a Ziplok bag. Place the bag into a wide mouth plastic or glass container – mark "hazardous waste clean-up."
  7. Mop: Thoroughly mop the area with a water detergent mixture.
  8. Test: Use indicator powder.

1. Spill response procedure for an acid chloride or acid anhydride spill:

Acid chlorides are not frequently used at EMU. However, anhydrides do get some use in the organic chemistry labs, and present particular cleanup challenges that typically merits specific planning that differs from other chemical classes. Acid chlorides and anhydrides are water reactive, so a similar procedure might be appropriate for other water reactive compounds, such as organo-metalic compounds. In the event of an acid chloride or acid anhydride spill:

1. 1. Open Acid Chloride kit (part of the bucket of spill kits, in each lab):
    1. Quart container of Oil Dry
    2. Quart size heavy duty plastic bag
    3. Fine bristle brush and plastic dust pan
    4. Handle as an acid, see below Acids
    5. Nitrile gloves, goggles, shoe covers
  2. Don PPE
  3. Cover the surface with Oil Dri
  4. Sweep up into a ziplock bag or other sealing container with a fine bristle brush (label container appropriately for waste disposal)
  5. Avoid water and avoid sodium bicarbonate
  6. Wipe contaminated surface with a dry paper towel

1. Spill response procedure for incidental spills of flammable liquids:

Flammable liquids are in frequent use at EMU, in both chemistry and biology. Fairly large containers (e.g. 1 gallon) of flammable liquids are often in the laboratory teaching spaces. Breakage or spillage of the full contents of one of these containers would be a serious undertaking to manage, and to clean up. Special training should be provided to any students who work with these containers.
Only personnel/students who have been trained in the Spill Response Procedures are to work with such chemicals after hours and then only if an equally trained "buddy" is in the area.
Some flammable organics are mildly toxic (e.g. acetone), while others can be highly toxic (formaldehyde). Thus, the main procedure can be followed for all flammable liquid spills, but there are some additional caveats (step v) to the procedure that should be followed for toxic flammable spills. When a spill of flammable liquids occurs, go through these steps:

1. 1. Can I do this? Use the chart below as a guide to determine the approach for cleaning up a spill of flammable liquids (Class I or Class II – see list).
    
    CATEGORY
    
    SIZE
    
    RESPONSE
    
    SMALL
    
    Up to 500 ml
    
    Absorbent
    
    LARGE
    
    More than 500 ml
    
    OUTSIDE HELP (call CHO, and/or (9-)911)
    
    The remainder of these guidelines applies to spills less than 500 ml.
  2. Evacuate the room and call for help
  3. Open flammable liquids spill kit (part of the bucket of chemical spill kits)
    1. "Pig" Stat-Mat, Heavy weight absorbent mat pads, 15"X20"
    2. Heavy duty, poly bags, gallon size
    3. folded paper towels for adsorbent.
    4. PPE: Goggles, Gloves (nitrile), shoe covers
    5. Barricade tape
  4. Don PPE
  5. For toxic volatile/flammable compounds (e.g. formaldehyde) use a respirator and ventless goggles – only personnel who have been trained and fitted through the EMU respiratory program through the EMU health center should do so. If the hazard properties of a chemical are unknown or an SDS is not available contact the Poison Control Center 1-800-222-1222.
  6. Barricade the room
  7. Prevent spark: Do not turn on or off any electrical equipment, including fans, ovens, etc…
  8. Move or remove all potential sources of ignition. Vapors tend to accumulate near the floor – remove electronics at floor level. Turn off natural gas flames.
  9. Ventilate the area using the fume hoods (they are always running). Activate the alarm on the fume hoods, upper right (in those labs with a standing hood) – this will increase the airflow through the hood, evacuating the room vapors more rapidly (an alarm will sound in the hood.) In some of the lab spaces, the snorkel hoods (they are also always running) should be opened with the side knob, and positioned over the spill.
  10. Absorb: Flammable liquids are best taken up through the use of spill pillows or pads. Because flammable liquid waste will generally be burned by the waste disposal service, do not use inert absorbents such as Oil Dri for an absorbent.
  11. Mop the spilled area by cleaning with a regular detergent and water.
PROCEDURES FOR CLEANING UP LARGE VOLUME HAZARDOUS CHEMICAL SPILL:

In the event where it is determined that necessary protective equipment and training are not available, that the cleanup cannot be done safely by the responsible faculty, staff person, nor the CHO, and to proceed would have a high probability of causing significant bodily harm, property or environmental damage, observe the following procedures, making the following contacts. These eventualities are broken down by the degree of danger/injury/damage incurred.
A. Imminent Danger with Serious Injuries or Threat of Injury, and/or Major Property Damage
Decontaminate any seriously injured subjects (safety shower, removal clothing) and move them from the source of injury, if this can be done without creating greater injury. (For any injury necessitating emergency transport to RMH where the victim was exposed to a chemical, 9-911 should be called to ensure adequate decontamination. The first responders will assess the injury, and coordinate transport to Sentara RMH.)
Contact:

When calling the Fire Department 9-911 give details of the accident, (chemical spill, fire etc.), location (Suter Science Center 1194 Park Road), hazardous material involved (have SDS available), injuries involved (nature and number.) Inform the dispatcher where you will be standing to direct them.
Chemical Hygiene Officer: 432-4420 (cell: 630-995-1955)
Coordinator of Safety and Security: 432-4396
EMU Health Center: 432-4308 (the health center will inform Human Resources and other others)

B. Minor Injuries or Illness, Moderate Property Damage
Contact:

Chemical Hygiene Officer – 432-4420
Coordinator of Safety and Security - 432-4396
EMU Health Center- 432-4308

***Depending on degree/definition of "moderate" property damage, it may be prudent to notify 9-911 for these incidents as well.
C. Minor Injuries or Illness, Minor Property Damage
Contact:

Chemical Hygiene Officer- 432-4420
EMU Health Center- 432-4308
Human Resource Center – 431-4148