CHEMICAL LABORATORY SAFETY

THE BIG SPILL - Spill Prevention and Cleanup

Objectives

The Big Spill - Spill Prevention and Cleanup: American Chemical Society chemical safety video courses

Important Concepts

For a complex spill, follow your organization's Chemical Hygiene and emergency response plans. A complex spill usually requires specially trained outside assistance.

For a flammable spill, turn off and remove all hot surfaces and ignition sources. Cover the spill with sorbent mats with a vapor-impervious backing to control fumes.

Collect and label all waste and cleanup materials, and keep them separate from regular lab waste. Consult your organization's safety officer on their proper disposal.

The ACS Guide for Chemical Spill Response Planning in Laboratories

PREFACE

The objective of this guide is to provide laboratory employees with a framework for spill response planning. This planning must be done in advance, not after a spill occurs.

All spills are different; this guide cannot give definitive guidance on how to handle every one. One thing is clear, however -- a professional response to spills, from planning to properly using cleanup equipment, will reduce the eventual costs (in injury, pollution, dollars, pride, and job security).

This guide is NOT a regulatory compliance manual. Many of the terms used in this guide have regulatory significance; however, this document refers to their common (not legal) meaning. Although this guide may be used in conjuction with your institution's regulatory compliance programs, it only provides an overview of technical considerations required to respond safely to laboratory spills.

Further, this guide is designed only to prepare laboratory workers for spill cleanup. Understanding this guide requires a basic level of chemical knowledge and training. If you do not have the basic knowledge to confidently make the decisions required, request assistance from others.

Reading this guide will help you, the laboratory worker, have fewer spills. It will also help you plan for an appropriate response when spills do occur.

Many spills in the laboratory work area can be prevented. Development and implementation of good laboratory practices will significantly reduce the likelihood of spills. While this guide is oriented to spill response, spill prevention methods are included as Appendix B.

DISCLAIMER

The material contained in this booklet has been compiled from sources believed to be reliable and to have expertise on the topic. This booklet is intended to serve as a starting point for spill response planning and management and does not purport to cover all related issues, specify minimum legal standards, or represent the policy of the American Chemical Society (ACS). All warranties (both expressed and implied), guarantees, and representations as to the accuracy or sufficiency of the information herein are hereby disclaimed, and the Society and its members assume no responsibility in connection herewith. Because of the rapidity with which the law changes and the many different laws to be found in various geographic areas, users of this booklet should consult pertinent local, state, and federal laws and regulations, and consult with legal counsel when implementing a laboratory waste management program and chemical spill response plan.

ACKNOWLEDGEMENTS

Every laboratory spill generates waste, so it is common for the members of the American Chemical Society's (ACS) Task Force on Laboratory Waste Management to worry about laboratory spills. This booklet is meant to help the bench chemist prevent and better respond to spills. It started as the idea of former Task Force member Jack Cole (DuPont, retired). The activities of the Laboratory Waste Management Task Force fall under the purview of the ACS Committees on Environmental Improvement and Chemical Safety.

Spills can seriously disrupt laboratory operations. Not only is valuable material lost, but a spill increasingly results in the temporary evacuation of a room or an entire building. For many reasons explained in this booklet, people have become more cautious when responding to laboratory spills.

In spite of our best efforts, spills happen. When they do, it makes sense to respond to them as carefully and efficiently as possible. The good news is that, for many laboratory spills, you may be able to safely clean them yourself. Not only does that save time, but your initiative demonstrates your accountability for maintaining a safe laboratory.

The Task Force would like to thank the ACS office of Government Relations and Science Policy for supporting this project. In particular, David C. Thomas supervised the booklet's writing and production and contributed his considerable editing talents. Kathleen A. Ream, Susan M. Turner, and Suzanne M. Baker also provided editorial review.

Thanks also to ACS Corporate Associates, who supported the booklet's preparation through a grant that funded an additional meeting dedicated to writing the booklet. Finally, thanks for the writing assistance of Luis E. Fernandez (University of Wisconsin-Madison) and Patricia A. Kandziora (University of Wisconsin, System Administration), two ACS members with substantial experience in laboratory safety issues.

Peter A. Reinhardt, Chair, ACS Task Force on Laboratory Waste Management

I. INTRODUCTION

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. This booklet will help you think logically about your potential spills and plan for a proper response.

In most cases, laboratory spills involve small quantities of materials and, if precautions are taken, present minimal hazards. Laboratory workers are usually the most appropriate people to clean up their spills because they

Some laboratory spills require outside assistance because of the spill's size or its unusual hazards. 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.

II. EMERGENCY PREPAREDNESS

To prepare for spills, you should:

Know Your Hazards

As an integral part of any laboratory work, you must identify the hazardous or potentially hazardous properties of all chemicals used or produced in your laboratory. Before using any chemicals, you should evaluate the consequences of potential spills and develop appropriate response procedures. If necessary, consult published data (such as material safety data sheets and chemical dictionaries) for response planning. Additionally, communicate potential hazards to other workers in your area.

When planning laboratory work and preparing for potential problems, determine the hazard class of all the chemicals to be used. The following chemical properties are of most concern when preparing for possible chemical spills:

Write Spill Response Procedures

Every laboratory should develop written spill response procedures. Such procedures should detail the initial steps to take when a spill occurs and include such elements as staff responsibilities, communication methods, instructions on using spill response equipment, and spill cleanup and residue disposal. Communicate these procedures to all individuals who use chemicals or who might assist during spill cleanup. Periodically review and update these procedures to ensure that all laboratory workers are familiar with the current information. Each procedure should indicate the date it was last reviewed. The laboratory's Chemical Hygiene Plan is a good place to include these procedures.

Spill response procedures should include elements such as

a listing of appropriate protective clothing, safety equipment, and cleanup materials required for spill cleanup (gloves, respirators, etc.) and an explanation of their proper use;

Make Materials and Equipment Available

Before starting any work with chemicals, verify that all necessary safety equipment and spill cleanup materials are available and in good working order. Additionally, ensure that the individuals who may be involved in spill response are properly trained in equipment use and spill cleanup procedures. Finally, regularly inspect all materials and equipment to ensure that they will function properly when needed.

The ABCs of Preparing For Laboratory Chemical Emergencies

Know Your Hazards

Write Spill Response Procedures

Make Emergency Response Equipment Available

III. FIRST STEPS WHEN A SPILL OCCURS: COMMUNICATION AND DETERMINATION

Whenever you spill a laboratory chemical or discover a spill or release, tell your colleagues and laboratory director--no matter how small or insignificant the spill or release appears. In order to assess a spill's risks and to obtain advice on cleanup procedures, it always helps to solicit the advice of others. Even a small spill can result in a harmful exposure to you or others or can result in hazards that are not obvious; therefore, notification of regulatory officials may be required.

When a spill occurs, you and others should move well away from the area when determining the appropriate response. There are two types of spills: simple spills, which you can clean up yourself, and complex spills, which require outside assistance. A simple spill is defined as one that

Three basic steps should be taken to determine whether a spill is simple or complex:

Evaluate the Risks

The first step in evaluating whether a spill is "simple" is to estimate the risks created by the spill. In spill response, the key risks of concern are human health effects, property damage, and environmental damage.

Potential health effects is the most important hazard category to consider when deciding whether or not to attempt a spill cleanup. Some chemical releases may result in health hazards such as fires or explosions. Other chemical releases may present health threats because of their ability to spread rapidly and enter the body readily. A spill is not " simple" if it presents these risks.

If the potential for fire or explosion exists, seek outside assistance from trained emergency responders. Releases of flammable chemicals (liquid or solid) can present significant fire and explosion risks when one or more of the following is present:

Toxic vapors and dust are also hazardous. Avoid direct contact with such hazards because they spread quickly, are easily absorbed through the skin, and may damage tissue.

A chemical spill is not a health risk if it has a low toxicity (especially if it is not volatile or a dust), is not highly corrosive, and is not a strong oxidizer. Such spills may be considered "simple" only if physical damage or environmental factors are absent. When a spilled chemical's toxicity is unknown, treat the spill like a potential human health hazard by avoiding exposure and seeking outside assistance.

The potential for physical damage to property (equipment, building materials, structures, or cleanup materials) also is important when determining whether you have a simple spill. Remember--a common first response to a spill is to try to protect equipment and property, but any real threat to such items will also threaten the persons cleaning up the spill. Do not attempt to protect property if there are any human health or fire/explosion hazards present.

In addition to potential fire and explosion hazards, strong corrosives and oxidizers typically fall under the property damage category. If any hazards are present that would damage property, treat the spill as complex and contact the appropriate authorities.

Some laboratory spills have the potential for escaping into the environment. Spills may release into the atmosphere, discharge into the sewer system, or leak directly into soils or surface water. While few laboratory spills present environmental threats, it is necessary to notify the appropriate authorities if a spill has the potential to cause environmental damage. If you can do so safely, it may be prudent to take the interim measures before the hazardous materials response team arrives, such as blocking a spreading spill with absorbents or covering a floor drain with a rubber mat.

Though small amounts of some chemicals pose environmental problems, most environmental risks are presented by large-quantity releases of materials. A large-quantity release that threatens the environment is not a simple spill, but requires the attention of trained responders.

Evaluate Quantities

The next step to take when determining whether a spill is "simple" is to evaluate the quantity of material released. If a spilled chemical is not hazardous, its cleanup (without the assistance of an emergency response team) is dependent on the ability to control the spill, as well as the availability of sufficient spill control materials (e.g., an absorbent for liquids). Factors that may complicate a cleanup effort (such as the unique characteristics of a spill's surroundings or the restricted access to a spill) must be determined on a case-by-case basis.

If the spilled chemical is hazardous, the threshold quantity for a simple spill cleanup depends on the spilled chemical's physical properties and hazards. This quantity depends on situational factors such as

The more toxic, corrosive, or flammable a material is, the less likely that the spill can be defined as "simple." Thresholds for flammable liquids and solids, as well as volatile toxics, should be relatively low. Spills of reactive chemicals should only be managed by trained responders (who may be in-house). In general, simple spill thresholds for liquids will be lower than the thresholds for non-volatiles.

Evaluate Potential Impacts

The third step to taken when deciding whether a spill can be managed as a simple spill is to evaluate the potential broader impacts of the spill. A chemical spill in an area where its potential risks are magnified by specific situations (such as physical situations or the presence of a large number of people) should not be managed as a simple spill. For instance, the presence of boxes, chemicals, and other ignition sources would magnify the impact of a one-gallon release of acetone. Since acetone is highly flammable and volatile, this situation would be immediately dangerous to both human health and property, and cleanup should be handled by an emergency responder. Other factors that may magnify a spill's impact and require emergency response are

When evaluating potential impacts, a prompt response can minimize adverse consequences. On the other hand, an inappropriate response can turn a simple spill into a complex situation.

To determine whether a spill is simple or complex (which is often the hardest part of spill response), you need to know

The following information will help you determine whether you have a simple spill:

Is It A Simple Spill?

(You can clean up most simple spills yourself.)

Does it Meet ALL Three Criteria of a Simple Spill?

Simple Spill

You can clean up yourself if

Get Help: This is Not a Simple Spill.

You probably need the help of a trained Hazardous Materials Emergency Response Team.

IV. RECOMMENDED PROCEDURES FOR CLEANING UP SIMPLE SPILLS

General Response Guidelines

For simple spills, emergency responders do not need to be notified. However, you should contact the environmental health and safety office or other responsible person within your facility. Most importantly, before cleaning up a simple spill, be sure that you can do so safely. You must have the right personal protective equipment, including, at a minimum, appropriate eye protection, protective gloves, and a lab coat. Additional protective equipment may be required for spills that present special hazards (such as corrosive or reactive spills or spills that have a splash potential). As a rule of thumb, if you need a respirator, you should request outside assistance because you do not have a simple spill.

The following steps should be taken during spill cleanup.

Special Precautions

The following precautions apply to chemicals that have hazardous characteristics. Note that some chemicals may exhibit more than one characteristic.

Remove all potential sources of ignition. Vapors are what actually burn, and they tend to accumulate near the ground.

Flammable liquids are best removed through the use of spill pillows or pads. Spill pads backed with a vapor barrier are available from most safety supply companies. Because flammable liquids will probably be incinerated, avoid using inert absorbents such as cat litter. All used absorbent materials should be placed in heavy-duty poly bags, which are then sealed, labeled, and disposed through your facility's hazardous waste management program. Before resuming work, make sure the spill area has been adequately ventilated to remove flammable vapors.

Use appropriate absorbent material to control the extent of the spill. Spill pillows or similar absorbent material usually work best because they do not have the dust associated with cat litter, vermiculite, or corn cobs. Place all used absorbent materials in heavy-duty poly bags. Seal the bags, label them, and hand them over to your facility's hazardous waste management program. Again, make sure the spill area has been adequately ventilated before resuming work.

Carefully select suitable personal protective equipment. Make sure all skin surfaces are covered and that the gloves you use protect against the hazards posed by the spilled chemical. Often it is a good idea to wear two sets of gloves: one as the primary barrier, the second as a thin inner liner in the event the primary barrier fails. When the cleanup is completed, be sure to wash hands and other potentially affected skin surfaces.

Mercury spills rarely present an imminent hazard unless the spill occurs in an area with extremely poor ventilation. The main exposure route of mercury is via vapor inhalation. Consequently, if metallic mercury is not cleaned up adequately, the tiny droplets remaining in surface cracks and crevices may yield toxic vapors for years.

When a mercury spill occurs, first cordon off the spill area to prevent people from inadvertently tracking the contamination over a much larger area. Generally, a special mercury vacuum cleaner provides the best method of mercury spill cleanup. DO NOT use a regular vacuum cleaner, because you will only disperse toxic vapors into the air and contaminate your vacuum cleaner. If a special mercury vacuum is not available, first use an appropriate suction device to collect the big droplets, then use a special absorbent (available from most laboratory supply vendors) to amalgamate smaller mercury droplets.

Ideally, mercury spills should be prevented in the first place. Examine all uses of mercury to see if substitutes are available. If substitutes are not available, use trays or other equipment to provide spill containment. Spilled mercury often accumulates in sink traps. Be prepared to contain the mercury when servicing such facilities.

Documentation

After cleaning up a spill, a simple write-up should be prepared to document what happened, why, what was done, and what was learned. Such documentation can be used to avoid similar instances in the future. Major incidents are almost always preceded by numerous near misses.

Laboratories seeking to minimize and prevent spills should consider the possible results of their choices and procedures. Such consideration should focus on reducing the likelihood of spills, as well as minimizing spill damage. experimental plans should only involve chemicals that are actually needed for the desired results. Ideally, laboratories should only store chemicals that will be used within a reasonable period of time. Additionally, correct chemical and experimental equipment choices must be made. Finally, the laboratory worker must not settle for inappropriate laboratory arrangements.

APPENDIX A. REGULATORY OVERVIEW

This appendix is intended to briefly describe regulations that may apply to laboratory chemical spills. Do not rely on this information for regulatory compliance purposes. Rather, consult the appropriate regulations directly.

Any chemical that presents a threat to the environment is defined by the Environmental Protection Agency (EPA) as a hazardous substance. The Agency assigns each hazardous substance a reportable quantity (RQ), which is based on a chemical's inherent risk properties. Virtually all common laboratory chemicals are on this hazardous substance list. While some hazardous substances have RQs as low as one pound, typical RQs are larger than the amounts found in laboratories. All chemical hazardous wastes have an RQ of one pound. A list of reportable quantities can be found in 40 CFR 302.4 (Code of Federal Regulations, Protection of Environment, Designation of Hazardous Substances).

Federal law requires reporting any hazardous substance spill or release that exceeds its RQ to the National Response Center (800-424-8802). State and local governments often have their own spill-reporting requirements, necessitating calls to state and local emergency response agencies as well.

All workers entering a laboratory must be trained (or be accompanied by a trained person) about the laboratory's chemical risks and the actions to be taken in an emergency. Additionally, the federal Occupational Safety and Health Administration (OSHA) requires all laboratories to develop a Chemical Hygiene Plan, which must include procedures to be used in the event of a spill. OSHA also requires laboratories to have evacuation plans.

Workers who clean up their own spills must be trained according to their laboratory's Chemical Hygiene Plan. This plan includes a written certification that all participants are trained on how to use their personal protective equipment. Workers who go into other work areas to assist with spills must be documented as having had additional, special training. Such training covers how to handle the specific material spilled, as well as how to approach hazardous material accidents in unfamiliar locations.

Preplanning with local emergency responders is required if a laboratory has "environmentally hazardous substances" exceeding threshold planning quantities. As with reportable quantities, threshold planning quantities vary according to each chemical's inherent hazards. Although few laboratories have sufficient quantities of hazardous chemicals to be subjected to these requirements, preplanning can help avoid miscommunication with local emergency responders. A list of threshold planning quantities is found in

40 CFR 355 (Emergency Planning and Notification) Appendices A and B.

Some spills require outside help from emergency responders because of the following:

Due to a third-party notification, or the miscommunication of a legal spill notification, emergency responders may arrive when their services are not necessary. Maintaining a good working relationship with your local emergency responders will help foster the mutual respect necessary to optimize spill response activities.

Cleanup materials from hazardous substance spills are regulated as hazardous waste. Follow your facility's guidelines for packaging, labeling, and disposing of these materials.

APPENDIX B. SPILL PREVENTION METHODS

Common examples of spill-causing incidents and associated prevention techniques are shown in Table B-1.

Laboratory spills can occur during a chemical's storage, transportation, or transfer, as well as in the actual experiment. A spill prevention program for storage areas should include the following:

To minimize spills during transport, a laboratory should integrate the following:

For the transfer of liquids from one container to another, the risk of spills can be reduced by

In addition to chemical spills, water spills can be caused by loose connections or breaks in lines to water condensers or cooling systems. Such spills can cause damage and inconvenience, even if they do not present environmental or health risks. Appropriate planning, including use of security clamps or other devices to prevent loosening of connections or automatic shut-off devices, can reduce the likelihood of flood damage. Occasionally, a laboratory may be affected by a leaking roof or a flood elsewhere in the building. Planning to prevent damage from incidents should include the protection of instruments that might be harmed by water. Similarly, storing chemicals and supplies so that they will not be touched by leaking water will minimize damage and inconvenience.

While considerable attention is given to potential spills or leaks of liquids, laboratories using gases should also develop spill prevention plans for these materials. Such plans should consider safety concerns related to securing tanks and other gas containers. Additionally, frequent checks of valves and tubing can be useful in spill and leak prevention. A laboratory should take care to prevent gas from escaping down a drain or up a fume hood.

Finally, pay attention to physical details in the laboratory, such as

Potential Cause of Spill

Prevention Technique
Container, such as a flask or beaker, tips over Secure containers and equipment to minimize the possibility of tipping.
Container dropping Keep containers and experimental equipment as low as possible.
Breaking a container or a piece of experimental apparatus Protect containers from breakage by keeping other items from falling on them.
A runaway reaction Plan experimental reactions to anticipate and to provide controls for undesired outcomes such as overheating.
Releases during transfer of materials from one container to another Pay attention to what you are doing. Provide secondary containment in the event of spills.
Holes and other leaks in transfer equipment such as pipes, hose, or valves Check for holes or leaks before use.
Placing material in an incompatible container Check for compatible uses of chemicals, particularly solvents or aggressive solutions. Check the material and construction of containers and equipment with a goal of maintaining structural integrity.
Breakage of thermometers or similar experimental equipment Select equipment that has reduced potential for breakage, e.g., replace mercury thermometers and electronic temperature device

Table B-1

APPENDIX C: RECOMMENDED COMPONENTS OF A LABORATORY CHEMICAL SPILL KIT

APPENDIX D: DECONTAMINATION

Decontamination is the process of physically removing or neutralizing contaminants that have accumulated on personnel and equipment; the last step of spill cleanup.

NOTE: The need for decontamination may be avoided by

The probability and extent of permeation is directly linked to the length of contact. The longer the contact, the more effort that will be required to decontaminate.