5 Management of Chemicals

5.A INTRODUCTION

5.B GREEN CHEMISTRY FOR EVERY LABORATORY

5.B.1 Prevent Waste

5.B.2 Microscale Work and Wet Chemistry Elimination

5.B.2.1 Design Less Hazardous Laboratory Processes and Reaction Conditions

5.B.3 Use Safer Solvents and Other Materials

5.B.4 Design Experimental Products for Degradation After Use

5.B.5 Include Real-Time Controls to Prevent Pollution

5.B.6 Minimize the Potential for Accidents

5.B.7 Green Chemistry Principles Avoid Multihazardous Waste Generation

5.B.8 Mercury Replacements in the Laboratory

5.B.8.1 Thermometers

5.B.8.2 Digital Thermometers

5.B.8.3 Differential Manometers

5.C ACQUISITION OF CHEMICALS

5.C.1 Ordering Chemicals

5.C.2 Receiving Chemicals

5.D INVENTORY AND TRACKING OF CHEMICALS

5.D.1 General Considerations

5.D.2 Exchange of Chemicals Between Laboratories and Stockrooms

5.D.3 Recycling of Chemicals and Laboratory Materials

5.D.3.1 General Considerations

5.D.3.2 Solvent Recycling

5.D.3.3 Recycling Containers, Packaging, and Labware

5.D.4 Labeling Commercially Packaged Chemicals

5.D.5 Labeling Other Chemical Containers

5.D.6 Labeling Experimental Materials

5.D.7 Use of Inventory and Tracking Systems in Emergency Planning

5.E STORAGE OF CHEMICALS IN STOCKROOMS AND LABORATORIES

5.E.1 General Considerations

5.E.2 Storage According to Compatibility

5.E.3 Containers and Equipment

5.E.4 Cold Storage

5.E.5 Storing Flammable and Combustible Liquids

5.E.6 Storing Gas Cylinders

5.E.7 Storing Highly Reactive Substances

5.E.8 Storing Highly Toxic Substances

5.F TRANSFER, TRANSPORT, AND SHIPMENT OF CHEMICALS

5.F.1 Materials of Trade Exemption

5.F.2 Transfer, Transport, and Shipment of Nanomaterials

5.F.2.1 Off-Site Transport and Shipments of Nanomaterials

5.F.2.2 On-Site Transfer and Transport of Nanomaterials



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5 Management of Chemicals 5.A INTRODUCTION 84 5.B GREEN CHEMISTRY FOR EVERY LABORATORY 84 5.B.1 Prevent Waste 84 5.B.2 Microscale Work and Wet Chemistry Elimination 84 5.B.2.1 Design Less Hazardous Laboratory Processes and Reaction Conditions 85 5.B.3 Use Safer Solvents and Other Materials 85 5.B.4 Design Experimental Products for Degradation After Use 86 5.B.5 Include Real-Time Controls to Prevent Pollution 86 5.B.6 Minimize the Potential for Accidents 87 5.B.7 Green Chemistry Principles Avoid Multihazardous Waste Generation 87 5.B.8 Mercury Replacements in the Laboratory 87 5.B.8.1 Thermometers 88 5.B.8.2 Digital Thermometers 88 5.B.8.3 Differential Manometers 88 5.C ACQUISITION OF CHEMICALS 88 5.C.1 Ordering Chemicals 88 5.C.2 Receiving Chemicals 89 5.D INVENTORY AND TRACKING OF CHEMICALS 90 5.D.1 General Considerations 90 5.D.2 Exchange of Chemicals Between Laboratories and Stockrooms 92 5.D.3 Recycling of Chemicals and Laboratory Materials 93 5.D.3.1 General Considerations 93 5.D.3.2 Solvent Recycling 93 5.D.3.3 Recycling Containers, Packaging, and Labware 93 5.D.4 Labeling Commercially Packaged Chemicals 94 5.D.5 Labeling Other Chemical Containers 94 5.D.6 Labeling Experimental Materials 94 5.D.7 Use of Inventory and Tracking Systems in Emergency Planning 94 5.E STORAGE OF CHEMICALS IN STOCKROOMS AND LABORATORIES 94 5.E.1 General Considerations 95 5.E.2 Storage According to Compatibility 96 5.E.3 Containers and Equipment 97 5.E.4 Cold Storage 98 5.E.5 Storing Flammable and Combustible Liquids 98 5.E.6 Storing Gas Cylinders 100 5.E.7 Storing Highly Reactive Substances 100 5.E.8 Storing Highly Toxic Substances 101 5.F TRANSFER, TRANSPORT, AND SHIPMENT OF CHEMICALS 101 5.F.1 Materials of Trade Exemption 102 5.F.2 Transfer, Transport, and Shipment of Nanomaterials 102 5.F.2.1 Off-Site Transport and Shipments of Nanomaterials 103 5.F.2.2 On-Site Transfer and Transport of Nanomaterials 104 83

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84 PRUDENT PRACTICES IN THE LABORATORY 5.A INTRODUCTION be confident that they have chosen procedures that minimize the quantities of chemicals to be used and This chapter organizes the discussion of managing minimize the disposal of hazardous materials. laboratory chemicals into six main topics: reducing Experiment planning in the culture of laboratory and eliminating the use and generation of hazardous safety includes minimization of the material used at substances (green chemistry); acquisition; inventory each step of an experiment. Consider two simple ex- and tracking; storage in stockrooms and laboratories; amples: (1) Transferring a liquid reaction mixture or recycling of chemicals and laboratory materials; and other solution from one flask to another container usu- transfer, transport, and shipment of chemicals. As ally requires the use of a solvent to rinse out the flask. Chapter 1 makes clear, prudence in these areas re- During this procedure, laboratory personnel should quires knowledge of the hazards posed by laboratory use the smallest amount of solvent possible that en- chemicals and the formulation of reasonable measures ables a complete transfer. (2) Celite is often used during to control and minimize the risks associated with their filtrations to keep the pores of filter papers or filter frits handling and disposal. Not all risk can be eliminated, from becoming clogged. When positioning the Celite, but through informed risk assessment and careful risk carefully determine the minimum amount needed to management, laboratory safety is greatly enhanced. be effective. Other examples of such strategies include Trained laboratory personnel, laboratory supervi- sors, and individuals who handle chemicals will find • considering how a reaction product will be used essential information in this chapter. Each person has and making only the amount needed for that use; an important role to play in a chemical’s life cycle at • appreciating the cost of making and storing un- an institution, and each one of them should be aware needed material; that the wise management of that life cycle not only • thinking about minimization of material used in minimizes risks to humans and to the environment each step of an experiment; but also decreases costs. Acknowledging this role and • searching for ways to reduce the number of steps giving it due consideration is one element of the culture in an experiment; of safety within a laboratory. • improving yields; • recycling and reusing materials when possible; 5.B GREEN CHEMISTRY FOR • coordinating work with co-workers who may be EVERY LABORATORY using some of the same chemicals (section 5.D.2); • considering the amount of reagents, solvents, and Green chemistry is the philosophy of designing hazardous materials used by automated labora- products and processes that reduce or eliminate the tory equipment when purchasing a new system; use and generation of hazardous substances, which fits • isolating nonhazardous waste from hazardous well with the overall goals of a culture of safety. The waste; and 12 principles of green chemistry (Anastas and Warner, • using a column purification system for recycling 1998) can be applied in the laboratory as guidelines of used solvent (section 5.D.3) for prudent experimental design and execution. Some of the principles are explained in more detail below, These steps are increasingly important because of the with examples of their broader application. A wealth changing requirements and economics of laboratory of green chemistry resources exists online in the form management. of reports, databases, and other Web applications and tools. These resources assist the development of green synthetic methods by providing information about the 5.B.2 Microscale Work and Wet Chemistry redesign of processes at the molecular level, the reduc- Elimination tion or elimination of the use of hazardous materials, One successful method of reducing hazards is to and the modification of chemical substances to make carry out chemical reactions and other laboratory pro- them safer. cedures on a smaller scale (i.e., microscale) when fea- sible. In microscale chemistry the amounts of materials 5.B.1 Prevent Waste used are reduced to 25 to 100 mg for solids and 100 to 200 μL for liquids, compared with the usual 10 to 50 Prudent laboratory chemical management begins g for solids or 100 to 500 mL for liquids. Smaller scale with adopting the first green chemistry principle of synthetic methods save money because they require waste prevention, which is considered before the or- less reagent and result in less waste. Of course, not all dering of the chemicals. When experiments have been laboratory procedures can be scaled down. Multigram carefully planned, trained laboratory personnel can laboratory preparation is often required to provide

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85 MANAGEMENT OF CHEMICALS 5.B.3 Use Safer Solvents and Other sufficient material for further work. Whether large Materials or small scale, exercise precaution appropriate to the scale, as well as the inherent hazards, of the procedure. Traditionally, chemists have chosen reagents and Similarly, in many cases instrumental analyses— materials to meet scientific criteria without always which require little reagent and generate very little giving careful consideration to waste minimization waste in themselves—can be substituted for wet chem- or environmental objectives. In synthetic procedures, istry. Consider the waste reduction inherent in spectro- overall yield and purity of the desired product are scopic organic analysis versus chemical derivatization. important factors, because better yield implies lower And, hazardous waste reduction also reduces both cost. On the other hand, material substitution can be compliance and disposal costs. When purchasing an important consideration in manufacturing process equipment to automate laboratory processes, choose design because of the large quantity, and potential cost, equipment that is efficacious for the job at hand, but of chemicals involved. The following questions should uses the least amount of reagents or solvents, or uses be considered when choosing a material to be used as a materials that are least hazardous. (See Vignette 5.1.) reagent or solvent in an experimental procedure: • Can this material be replaced by one that will 5.B.2.1 Design Less Hazardous Laboratory expose the experimenter, and others who handle Processes and Reaction Conditions it, to less potential hazard? The third principle of green chemistry suggests that, • Can this material be replaced by one that will where possible, syntheses should be designed using reduce or eliminate the hazardous waste and the less toxic reagents. Although the use of a toxic reagent resulting cost of waste disposal? does not necessarily imply generation of a toxic waste, • Can these steps be taken in conjunction with yield in line with the first principle, chemists should evalu- maximization and minimization of overall waste ate potential sources of hazardous waste expected from and cost? the proposed synthesis and incorporate strategies to minimize them. All things being equal, laboratories are safer when they substitute nonhazardous, or less hazardous, chemicals where possible by considering alternative VIGNETTE 5.1 synthetic routes and alternative procedures for work- Pollution prevention ing up reaction mixtures. The following additional reduces solvent waste examples illustrate the application of this principle to common laboratory procedures: A pollution prevention assessment of one or- ganic chemistry research laboratory at a univer- • To reduce the amount of copper released to the sity revealed that each of the 25 researchers in the sewer, use iron complexes rather than copper group used 1 L of solvent, usually acetone, every when studying spectrophotometry in general week to clean and/or rinse glassware, spatulas, chemistry. and other items used in their procedures. For • In liquid scintillation counting of low-level radio- example, a researcher might rinse a spatula with active samples, where possible, use nonflamma- acetone at the end of a procedure or use a solvent ble, lower toxicity, water-miscible solvents rather to speed the drying process after cleaning with than xylene, toluene, or dioxane, so as to eliminate soap and water. The excuses for using the solvent fire hazard and waste that must be incinerated. ranged from not having enough glassware avail- • Substitute solid or liquid reagents for hazardous able (thus the need to expedite drying) to lack gases that must be used at elevated pressure. of good brushes for cleaning residue to simply As an example, phosgene is a highly toxic gas taking a shortcut to the cleaning process. occasionally used as a reagent in organic trans- The lab purchased more glassware, better formations. Its use requires proper precautions brushes, and an ultrasonicator that uses a mild to contain the gas and handle and dispose of detergent. The savings in solvent purchase and cylinders. Commercially available products such disposal paid back the price of the new pur- as diphosgene (trichloromethyl) chloroformate, chases within 3 months. Later, the lab installed a liquid, or triphosgene bis(trichloromethyl) under-the-bench lab dishwashers, which re- carbonate, a low-melting solid, are often substi- sulted in even further reductions in solvent use tuted for phosgene by appropriate adjustment of for cleaning. experimental conditions or are used to generate

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86 PRUDENT PRACTICES IN THE LABORATORY phosgene only on demand. Both chemicals are ized equipment for handling, but because of the highly toxic themselves, and their use in any event ubiquity of chromatography methods operating should be considered carefully, but solids avoid at elevated pressure and the common nature of the problems associated with handling a toxic gas. the pumps and vessels necessary, much of the • Consider carefully the use of reagents contain- hazard has been mitigated. The technology for ing toxic heavy metals. For example, proprietary using supercritical fluids has developed rapidly detergents for glassware (used, if necessary, with in recent years. Consider use of these materials, ultrasonic baths) are a safer substitute for chromic but with appropriate precaution and dedicated acid cleaning solutions. Various chromium(VI) permanent equipment. and other metal oxidants have been important in synthetic organic chemistry, but other oxidants are 5.B.4 Design Experimental Products for possible substitutes. When planning a reaction, Degradation After Use consider the cost of disposal of heavy metal waste in addition to its utility. Search the literature for Green chemistry practitioners plan synthesis and other oxidation reagents tailored to the specific other processes so that, as part of the experiment, the needs of a given transformation. (For information products and byproducts are rendered safe or less haz- about reducing the use of mercury in laboratory ardous. For example, they include in the experimental equipment, see section 5.B.8.) plan reaction workup steps that deactivate hazardous • F -TEDA-BF4, or 1-chloromethyl-4-fluoro-1,4- materials or reduce their toxicity. diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), substitutes for more hazardous reagents in many 5.B.5 Include Real-Time Controls to fluorination procedures. To reduce the reactiv- Prevent Pollution ity and toxicity risks associated with perchloryl fluoride, fluorine, and other fluorinating reagents, To cut costs, firms are increasingly asking for just- search the literature for appropriate substitutes. in-time delivery of raw materials and using other real- • Avoid solvents listed as select carcinogens (for a time controls. Green chemistry laboratories can borrow definition of select carcinogens, see Chapter 4, sec- this strategy. A quantity of hazardous chemical not or- tion 4.C.3.4), reproductive toxins, or hazardous air dered is one to which trained laboratory personnel are pollutants. Choose solvents with relatively high not exposed, for which appropriate storage need not American Conference of Governmental Industrial be found, which need not be tracked in an inventory Hygienists threshold limit values. Recognizing control system, and which will not end up requiring that not all hazards can always be reduced si- costly disposal when it becomes a waste. multaneously, the best substitute solvent meets Part of acquiring a chemical is a life-cycle analysis. needed experimental constraints but has physio- All costs associated with the presence of each chemical chemical properties, such as boiling point, flash at an institution must be considered. The purchase cost point, and dielectric constant that are similar to is only the beginning; the handling costs, human as the original solvent. Although cost can be a fac- well as financial, and the disposal costs must be taken tor, consider the benefits of safety, health, and into account. Without close attention to these aspects the environment as well. For example, heptane is of managing chemicals in a laboratory, orders are not more costly than hexane, but is very similar phys- likely to be minimized, and unused chemicals become iochemically and is not listed by the U.S. Environ- a significant fraction of the laboratory’s hazardous mental Protection Agency (EPA) as a hazardous waste. air pollutant. Toluene usually can substitute for The American Chemical Society’s booklet Less Is Bet- the carcinogen benzene. Chemical suppliers now ter: Laboratory Chemical Management for Waste Reduction highlight solvents with lower hazards including (Task Force on Laboratory Waste Management, 1993) reduced flammability and potential for peroxide gives several reasons for ordering chemicals in smaller formation. containers, even if that means using several containers • Supercritical fluids present an interesting case in of a material for a single experiment: conflicting green chemistry principles. Supercriti- cal CO2 as a solvent involves a chemically rela- • Consequence of breakage is substantially reduced tively benign material, carbon dioxide. Reaction for small package sizes. workup requires only ambient heat, and there • Risk of accident and exposure to hazardous mate- is no hazardous waste. On the other hand, it re- rial is less when handling smaller containers. quires elevated pressure. Supercritical solvents for • Storeroom space needs are reduced when only a chromatography and synthesis require special- single size is inventoried.

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87 MANAGEMENT OF CHEMICALS 5.B.7 Green Chemistry Principles Avoid • Containers are emptied faster, resulting in less Multihazardous Waste Generation chance for decomposition of reactive compounds. • Use of the so-called “economy size” often dictates Because the management of multihazardous waste a need for other equipment, such as transfer con- is often difficult, prudent green chemistry principles tainers, funnels, pumps, and labels. Added labor minimize its generation. Chapter 8, sections 8.C.2 to subdivide the larger quantities into smaller and 8.C.3, provides information on eliminating or containers, as well as additional personal protec- minimizing the components of waste that are biologi- tive equipment for the hazards involved, also may cal or radioactive hazards, respectively. For chemical– be needed. In most cases, it is safer, and may be biological waste, the primary strategy for minimizing less costly, to allow commercial providers to break the multihazardous waste is to maintain segregation bulk rather than “doing it yourself.” of chemical and biological waste streams as much as • If unused hazardous material must be disposed possible. For reduction of radioactive hazards, the o f, the disposal cost per container is less for strategies discussed include substituting nonradioac- smaller containers. tive materials for radioactive materials, substituting radioisotopes having shorter decay times (e.g., when An institution should also minimize the amount radioactive iodine is specified, using iodine-131, with a of chemical accepted as a gift or as part of a research half-life of 8 days, instead of iodine-125, with a half-life contract. More than one laboratory has been burdened of 60 days), and carrying out procedures with smaller with the cost of disposing of a donated chemical that amounts of materials. was not needed. Donated material can easily become a liability. A 5.B.8 Mercury Replacements in the chemical engineering researcher accepted a 55-gallon Laboratory drum of an experimental diisocyanate as part of a re- search contract. The ensuing research project used less Chronic exposure to mercury (Chemical Abstracts than 1 gallon of the material, and the grantor would Service [CAS] No. 7439-97-6) through any route can not take the material back for disposal. No commer- produce central nervous system damage (Mallinkrodt cial incinerator would handle the material in its bulk Baker, Inc., 2008). Common exposure routes include form. The remaining material had to be transferred to inhalation, ingestion, and skin or eye contact. Ther- 1-liter containers and sent as lab packs for disposal, at mometers and manometers are the most common labo- significant cost. ratory uses of elementary mercury, and in many cases, In section 5.D.2, the exchange or transfer of chemi- there are suitable nonmercury alternatives available. cals to other trained laboratory personnel is discussed. Broken thermometers and manometers create a health Smaller containers increase the chance that chemicals to hazard in the laboratory and, where possible, should be transferred are in sealed containers, which increases be replaced with mercury-free substitutes. the receiver’s confidence that the chemicals are pure. The consequences of broken mercury-filled equip- ment (thermometers, manometers, diffusion pumps, bubblers, etc.) can include personnel exposure, labo- 5.B.6 Minimize the Potential for Accidents ratory and environmental contamination, mercury Green chemistry also means designing to reduce spill cleanup, and disposal of mercury and mercury- accidents, injuries, and exposures to laboratory, store- contaminated debris. Mercury spills are challenging to room, and receiving personnel. Chapters 4 and 6 clean up completely and require training and special explain planning and risk assessment for laboratory spill control materials (see Chapter 6, section 6.C.10.8, personnel. Be sure that hazardous properties are un- for more information about mercury spill cleanup). derstood before a material is purchased, synthesized, Elemental mercury is very heavy and can be expensive or otherwise acquired. Search references and the lit- to dispose as waste (Foster, 2005a). Replacing mercury- erature to be cognizant of the properties of explosivity, filled equipment in the laboratory ensures compliance water and air reactivity, instability, age-related degra- with 2 of the 12 principles of green chemistry: No. 1, dation, and pressurization when contained. Searches of “Prevent Waste: Design chemical syntheses to prevent historical laboratory accident data reveal risks associ- waste, leaving no waste to treat or clean up”; and ated with experimental setups, procedures, equipment, No. 12, “Minimize the potential for accidents: Design facilities, inadequate training, and noncompliance with chemicals and their forms (solid, liquid, or gas) to safety rules. Trained laboratory personnel with this minimize the potential for chemical accidents includ- knowledge should communicate it to co-workers and ing explosions, fires, and releases to the environment” material handling personnel. New laboratory person- (Anastas and Warner, 1998). nel deserve a special orientation.

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88 PRUDENT PRACTICES IN THE LABORATORY the temperature being measured and the remainder of 5.B.8.1 Thermometers the stem is exposed to the ambient temperature. Par- Design a mercury thermometer replacement pro- tial immersion thermometers are clearly marked with gram to provide safe, suitable substitutes for use in a permanently placed line on the stem to indicate the laboratories. Factors that should be considered during proper immersion depth (ASTM International, 2007a). the mercury replacement process are various applica- In addition to thermometers that are filled with tions in the laboratories, required temperature range, mercury-alternative liquids, long-stem digital ther- thermometer length, immersion depth, scale divisions, mometers are available with probes that are resistant cost, accuracy in relation to application, and durability to most laboratory chemicals, including acids, bases, upon exposure to corrosive solutions. In some cases, and solvents. The bright displays, usually ¼ in. high, these alternative thermometers have a more limited are easy to read and display the temperature in both temperature range than a mercury thermometer. degrees Fahrenheit and degrees Celsius, with ranges Perform tests for accuracy in the laboratory prior to a from −58 to 302 °F and –50 to 150 °C. Long-stem ther- total replacement program to ensure that the mercury mometers are constructed of plastic and stainless steel substitutes will be suitable for the methods that will be and do not contain glass or mercury, which make them employed in that particular laboratory. To ensure accu- ideal thermometers for use in academic laboratories. racy, thermometers must be calibrated using approved The stems are generally 8 inches long with an overall methods such as ASTM E 77 (ASTM International, thermometer length of 11 in. 2007a) and must be traceable to the National Institute of Standards and Technology (NIST). There is a wide selection of mercury-free liquid-filled 5.B.8.2 Digital Thermometers thermometers available, including spirit thermometers Where a mercury thermometer is the only option, (filled with biodegradable petroleum-based mineral armor cases, which protect against breakage without spirits and dyes) and alcohol-based thermometers. affecting accuracy, or Teflon-coated mercury thermom- When broken, these thermometers present no hazard- eters are recommended. These are particularly useful ous material disposal problems. Some spirit thermom- in high-temperature ovens, oil baths, and autoclaves, eters had a history of the thread breaking more easily where cleaning up a mercury spill can be challenging than a mercury thermometer, but many of the newer and the spill creates a serious health hazard. formulations have overcome this problem. In the event that the thread breaks, the simplest and safest method to reunite the liquid is to use a centrifuge. Carefully 5.B.8.3 Differential Manometers insert the thermometer, bulb down, in the centrifuge. Depending on the measurement range, labs can Use cotton wadding at the bottom of the cup to prevent substitute water or calibrated oils for mercury. Pressure any damage to the bulb. Turn on the centrifuge and in transducers or electronic pressure gauges may also be just a few seconds all the liquid will be forced past the an alternative to a conventional manometer. separation. Note that if the cup is not deep enough, and all the centrifuge force is not below the column, the column will split, forcing half the liquid in the bulb and 5.C ACQUISITION OF CHEMICALS half the liquid in the expansion chamber (Izzo, 2002). For liquid-filled thermometers used to measure the 5.C.1 Ordering Chemicals temperature of liquids, accuracy will also depend on Authority to place orders for chemicals may be cen- choosing the correct immersion depth. This is less of tralized in one purchasing office or may be dispersed to an issue for mercury thermometers because mercury varying degrees throughout the institution. The advent generally has better thermoconductivity. A total im- of highly computerized purchasing systems, and even mersion thermometer is designed to indicate tem- online ordering, has made it feasible to allow ordering peratures correctly when the bulb and all but 12 mm of at the departmental or research group level. However, the liquid column are immersed in the bath medium. the ability to control ordering of certain types of ma- The top 12 mm of the liquid column should be above terials through a central purchasing system (e.g., pro- the bath medium so that the thermometer can be read hibiting flammables in containers over a certain size or and the material does not distill at high temperatures. ensuring appropriate licensing of radioactive material Thermometers that have been graduated for total im- users) is almost completely lost when the purchasing mersion usually have no markings on the back pertain- function is decentralized. In these cases, other creative ing to immersion. A partial immersion thermometer is ways of exercising control need to be found. designed to indicate temperatures correctly when the Before purchasing a chemical, prudent laboratory bulb and a specified portion of the stem are exposed to personnel ask several questions:

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89 MANAGEMENT OF CHEMICALS • Is the material already available from another lab- ing a reagent and creating an unnecessary waste oratory within the institution or from a surplus- of material and time. Some materials may require chemical stockroom? If so, waste is reduced, and express or overnight delivery and will not tolerate the purchase price is saved. The tendency to use being held in transit over a weekend or holiday. only new chemicals because of their purity should • Can the waste be managed satisfactorily? A chemi- be scrutinized, and that tendency should be care- cal that produces a new category of waste may fully justified to ensure that materials already on cause problems for the waste management pro- hand are used whenever possible. gram. An appropriate waste characterization and • What is the minimum quantity that will suffice method for proper disposal should be identified for current use? Chemical purchases should not before the chemical is ordered. be determined by the cheaper unit price basis of large quantities but rather by the amount needed Within an institution or organization, one of the for the experiment. The cost of disposing of the advantages of computerization of ordering is that infor- excess is likely to exceed any potential savings mation about deliveries of chemicals can be retrieved gained in a bulk purchase (i.e., the cost of getting from the chemical supplier, which provides a clear rid of a chemical may exceed its acquisition cost). picture of the purchasing history and distribution of If a quantity smaller than the minimum offered by chemicals across buildings. Some institutions include a supplier is needed, the supplier should be con- in their annual contracts with suppliers a requirement tacted and repackaging requested. Compressed to report on a monthly, a quarterly, or an annual basis gas cylinders, including lecture bottles, should the quantity of each type of chemical purchased and the normally be purchased from suppliers who accept location to which it was delivered. This information can return of empty cylinders. If paying demurrage be helpful in preparing the various annual reports on charges, the laboratory may want to return par- chemical use that may be required by federal, state, or tially filled cylinders that will not be used in the local agencies. For example, centralized ordering may near future. assist the institution in complying with the Controlled • What is the maximum size container allowed in Substances Act and with CFATS. In addition, such a the areas where the material will be used and system is also useful for tracking the use of flammables, stored? Fire codes and institutional policies regu- locations of Food and Drug Administration drug pre- late quantities of certain chemicals, most notably cursors, and DHS chemicals of interest. [See Handbook of flammables and combustibles. For these materi- Chemical Health and Safety (Alaimo, 2001); Code of Federal als, a maximum allowable quantity for laboratory Regulations, 1998.] storage has been established (see also sections A purchase order for a chemical should include a 5.E.5 and 5.E.6). request for a material safety data sheet (MSDS). How- • Can the chemical be managed safely when it ar- ever, many of the larger laboratory chemical suppliers rives? Does it require special storage, such as in a send each MSDS only when an organization first orders drybox, refrigerator, or freezer? Do receiving per- the chemical. Subsequent orders of the same chemical sonnel need to be notified of the order and given are not accompanied by the MSDS. Therefore, a central special instructions for receipt? Will any special network of accessible MSDSs should be established. equipment necessary to use the chemical be ready This collection of MSDSs can be electronic if computer when it arrives? An effort should be made to order access is available to all employees at all times. chemicals for just-in-time delivery by purchasing all unstable or extremely reactive materials from 5.C.2 Receiving Chemicals the same supplier with a request for one delivery at the best time for performing an experiment. Chemicals arrive at institutions in a variety of ways, • Does the chemical present any unique security including U.S. mail, commercial package delivery, ex- risks? Is it a controlled substance? Is there a risk press mail services, and direct delivery from chemical of potential intentional misuse of the chemi- warehouses. Deliveries of chemicals should be con- cal? Will the quantity ordered affect compliance fined to areas that are equipped to handle them, usually with the U.S. Department of Homeland Security a loading dock, receiving room, or laboratory. Proper (DHS) Chemical Facility Anti-Terrorism Standard equipment for receipt of chemicals includes chains (CFATS)? (See Chapter 10 for a discussion of labo- for temporarily holding cylinders and carts designed ratory security.) to safely move various types of chemical containers. • Is the chemical unstable? Inherently unstable Shelves, tables, or caged areas should be designated for materials may have very short storage times and packages to avoid damage by receiving room vehicles. should be purchased just before use to avoid los- Chemical deliveries should not be made to depart-

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90 PRUDENT PRACTICES IN THE LABORATORY mental offices because, in general, offices are unlikely or suppliers should be used. Original purchase order to be equipped to receive these packages. However, if should specify delivery criteria. Some examples of de- delivery to such an office is the only option, a separate livery criteria would be that the gas cylinder must have undisturbed location, such as a table or shelf, should a cap and the cap must not be stuck, and damaged con- be identified for chemical deliveries, and the person tainers may not be accepted without the inspection and ordering the material should be notified immediately approval of a technically qualified individual on-site. on its arrival. When packages are opened in the laboratory, labora- Receiving room, loading dock, and clerical personnel tory personnel should verify that the container is intact should to be trained adequately to recognize hazards and is labeled, at a minimum, with an accurate name that may be associated with chemicals coming into the on a well-adhered label. For unstable materials, and facility. They need to know what to do if a package is preferably for all materials, the date of receipt should leaking or if there is a spill in the receiving facility, and be on the label. Labels placed by the manufacturer they need to know who to call for assistance when a should remain intact. New chemicals should be entered problem develops. They should also be trained to iden- into the laboratory’s inventory promptly and moved to tify activity that could suggest a security risk, such as the appropriate storage area. unauthorized personnel near the loading dock or un- warranted interest in their activities. The Department 5.D INVENTORY AND TRACKING of Transportation (DOT) requires training for anyone OF CHEMICALS involved in the movement of hazardous materials, including individuals who have been designated to 5.D.1 General Considerations receive hazardous materials on behalf of the organiza- tion (see Chapter 11, sections 11.E.1.5, and 11.F.1). Prudent management of chemicals in any laboratory Your firm or institution should decide if stockroom is greatly facilitated by keeping an accurate inventory or laboratory personnel are responsible for unpacking of the chemicals stored. An inventory is a record (usu- incoming chemicals. Incoming packages should be ally a database) that lists the chemicals in the labora- promptly opened and inspected to ensure that con- tory, along with information essential for their proper tainers are sealed in good condition and to confirm management. Chemical inventories are also a vital tool, what was ordered. The unpacked chemicals should be and in some cases are required, for maintaining regula- stored safely. In particular, reactive chemicals shipped tory compliance. An organization cannot adequately in metal containers (e.g., lithium aluminum hydride, manage safety, security, emergency planning, waste sodium peroxide, phosphorus)—which are often disposal, and the like without knowing what chemicals sealed—must be promptly unpacked and stored to are on-site and where they are stored. Without an up- prevent degradation and corrosion and to be available to-date inventory of chemicals, many important ques- for periodic inspection. tions pertinent to prudent management of chemicals Transportation of chemicals within the facility, can be answered only by visually scanning container whether by internal staff or outside delivery personnel, labels. A well-managed inventory system promotes must be done safely. Single boxes of chemicals in their economical use of chemicals by making it possible to original packaging can be hand carried to their destina- determine immediately what chemicals are on hand. tion if they are light enough to manage easily. Groups An inventory is not limited to materials obtained from of packages or heavy packages should be transported commercial sources but includes chemicals synthe- on a cart that is stable, has straps or sides to contain sized in a laboratory. If a chemical is on hand, the time packages securely, and has wheels large enough to and expense of procuring new material are avoided. In- negotiate uneven surfaces easily. Suitable carriers (e.g., formation on chemicals that present particular storage secondary containment) should be used when trans- or disposal problems facilitates appropriate planning porting individual containers of liquids. for their handling. Although a detailed list of hundreds Cylinders of compressed gases should always be or thousands of chemicals stored in a particular loca- secured on specially designed carts and never be tion may not be directly useful to emergency respond- dragged or rolled. The cap should always be securely in ers, it can be used to prepare a summary of the types place. Whenever possible, chemicals and gas cylinders of chemicals stored and the hazards that might be should be moved on freight elevators that are not used encountered. In larger organizations where chemicals for public occupancy, especially when moving toxic, are stored in multiple locations, the inventory system cryogenic, or asphyxiating gases. should include the storage location for each container If outside delivery personnel do not handle materi- of each chemical. An inventory system is also of use als according to the receiving facility’s standards, im- when considering laboratory security concerns. It can mediate correction should be sought, or other carriers assist in ensuring compliance with regulations, such

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91 MANAGEMENT OF CHEMICALS as CFATS (see Chapter 10), tracking of materials to such a card file is limited by its size and the order in ensure that they are not intercepted en route, and in which it is sorted. This type of system has obvious identification of unusual orders within the department advantages in terms of simplicity and low cost, but it or organization. suffers several limitations. Listings of chemicals must If procedures for the facile updating of information be prepared manually, and the integrity of the database on storage locations are developed, the system be- depends on how well the card file is maintained. comes a tracking system. Such a system promotes the For an inventory of more than a few hundred chemi- sharing of chemicals originally purchased by different cals, a computer-based system offers advantages. Many research groups or laboratories. The more laboratories spreadsheet and database programs maintain an ef- in an organization agree to share chemicals, the greater fective chemical inventory system, cross-referenced the likelihood that items unneeded in one location will by different scientific or common names. The integrity be used elsewhere. Tracking systems are more complex of the inventory system is enhanced by the ease of to establish than simple inventories and require more making backup copies of the database. Searches for effort to maintain, but their favorable impact on the desired chemicals are carried out in a number of ways, economics and efficiency of chemical use in a large depending on the software. The ability to search and organization often justify their use. sort the database, for example, by hazard classification, Each record in a chemical inventory database gener- acquisition date, owner, or other parameters, and to ally corresponds to a single container of a chemical prepare lists of the results of such a sort contribute to rather than merely to the chemical itself. This approach efficiency in a variety of chemical management tasks. allows for a more logical correspondence between the Section 5.C.1 notes the prudence of establishing a cen- records in the database and the chemicals stored in the tral network of MSDSs. Including MSDSs and labora- laboratory. The following data fields for each item are tory chemical safety summaries (LCSSs) (see Chapter recommended for any system: 4 and accompanying CD) in the inventory’s database is highly desirable. Alternatively, the inventory could • name as printed on the container; be linked to other databases containing safety and • molecular formula, for further identification and environmental information about the chemicals. The to provide a simple means of searching; quality of MSDSs varies significantly from one manu- • CAS registry number, for unambiguous identi- facturer to another. LCSSs, which are targeted to the fication of chemicals despite the use of different needs of typical trained laboratory personnel, are a use- naming conventions; ful supplement to the information provided by MSDSs. • source; and Having a fully capable chemical tracking system de- • size of container or original quantity of chemical. pends on careful selection of database software. Such a package should permit access from multiple terminals In addition, the following information may be useful: or networked computers and, most importantly, have a foolproof efficient method for rapidly recording the • hazard classification, as a guide to safe storage, physical transfer of a chemical from one location to handling, and disposal; another. Bar-code labeling of chemical containers as • date of acquisition, to ensure that unstable chemi- they are received provides a means of rapid error-free cals are not stored beyond their useful life; entry of information for a chemical tracking system. If • storage location, in laboratories where multiple reagent chemical suppliers were to adopt a system in locations exist; and which chemical containers were labeled with bar codes • on-site owner or staff member responsible for the providing essential information on their products, the sample. maintenance of chemical tracking systems would be greatly facilitated. Proprietary software packages for In a chemical tracking system, how the consumption tracking chemicals are available. Organizations oper- of chemicals is tracked must be considered. The effort ating under good laboratory practice regulations may involved in maintaining data on the precise contents of even want to track the quantity of material in each each container must be weighed against the potential container. The investment in hardware, software, and benefit such a system would provide. Many tracking personnel to set up and maintain a chemical inventory systems omit this information and record only the tracking system is considerable but pays significant container size. dividends in terms of economical and prudent man- A simple inventory system records the above infor- agement of chemicals. mation for each container on index cards, which are As with any database, the usefulness of an inventory then kept in an accessible location in some logical order, or chemical tracking system depends on the integrity such as by molecular formula. The ease of searching of the information it contains. If an inventory system

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92 PRUDENT PRACTICES IN THE LABORATORY is used to locate chemicals for use or sharing in the vation or relocation. Try to avoid receiving en- laboratory, even a moderate degree of inaccuracy tire chemical inventories from decommissioned erodes confidence in the system and discourages use. laboratories and do not donate entire chemical The need for high fidelity of data is greater for a track- inventories to schools or small businesses. ing system, because trained laboratory personnel will rely on it to save time locating chemicals rather than Chemical inventory challenges have not changed physically searching. For these reasons, appropriate since the first use of index card files. The initial chal- measures should be taken periodically to purge any in- lenge is ensuring that every laboratory chemical gets ventory or tracking system of inaccurate data. A physi- entered into the inventory. This task often requires the cal inventory of chemicals stored, verification of the concerted effort of many staff members. The second data on each item, and reconciliation of differences are challenge is keeping the inventory current. Meeting performed annually. This procedure coincides with an this challenge usually requires designating one or more effort to identify unneeded, outdated, or deteriorated responsible individuals to enter new materials into the chemicals and to arrange for their disposal. The follow- system; these individuals are the only personnel who ing guidelines for culling inventory may be helpful: should have write/edit access to the inventory. Facil- ity procedures must make sure that notice of all new • Consider disposing of materials not expected to materials is presented to these designated individu- be used within a reasonable period, for example, als for entry into the inventory. Assuming that every 2 years. For stable, relatively nonhazardous sub- staff member will faithfully enter new chemicals into stances with indefinite shelf lives, a decision to the system results in an obsolete inventory. A third retain them in storage should take into account challenge is making sure that consumed chemicals, their economic value, scarcity, availability, and that is, empty containers, are removed from the active storage costs. inventory. • Make sure that deteriorating containers or con- Inventories are valuable to laboratory operations if tainers in which evidence of a chemical change everyone supports and contributes to the inventory. in the contents is apparent are inspected and Managers with budgetary responsibilities appreciate handled by someone experienced in the possible the value of an established inventory system in reduc- hazards inherent in such situations. ing procurement and operating costs. Laboratory waste • Dispose of or recycle chemicals before the expira- coordinators favor more efficient use of in-house mate- tion date on the container. rials resulting in reduced quantities of waste. • Replace deteriorating labels before information More information about chemical management sys- is obscured or lost to ensure traceability and ap- tems can be found in Chapter 2, section 2.D.4. propriate storage and disposal of the chemicals. • Because many odoriferous substances make their 5.D.2 Exchange of Chemicals Between presence known despite all efforts to contain Laboratories and Stockrooms them, aggressively purge such items from storage and inventory. The exchange or transfer of chemicals between labo- • A ggressively cull the inventory of chemicals ratories at an institution depends on the kind of inven- that require storage at reduced temperature in tory system and central stockroom facilities in place. environmental rooms or refrigerators. Because Some institutions encourage laboratory personnel to these chemicals may include air- and moisture- return materials to the central stockroom for redistribu- sensitive materials, they are especially prone to tion to others. The containers are sealed or open with a problems that are exacerbated by the effects of portion of the material used. Containers that have been condensation. opened are often of sufficient purity to be used as is in • Dispose of all hazardous chemicals at the comple- many procedures. If the purity is in doubt, the person tion of the laboratory professional’s tenure or who returned the material should be consulted. The transfer to another laboratory. The institution’s stockroom personnel can update the central inventory cleanup policy for departing laboratory research- periodically to indicate what is available for exchange ers and students should be enforced strictly to or transfer. For an exchange program to be effective, all avoid abandoned unknowns that pose unknown contributors to and users of the facility must reach a hazards to remaining personnel and have high consensus on the standards to be followed concerning disposal costs. the labeling and purity of stored chemicals. • Develop and enforce procedures for transfer or A word of caution is offered in regard to surplus- disposal of chemicals and other materials when chemical stockrooms; they must be managed with the decommissioning laboratories because of reno- same degree of control as a new-chemical storage area.

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93 MANAGEMENT OF CHEMICALS The surplus-chemical stockroom is not a depository for More information about this regulation can be found any chemical that will not be wanted in the laboratory in Chapters 8 and 11. State and local regulations must within a reasonable period (e.g., 2 to 3 years); such also be considered. materials are to be disposed of properly. Rooms that Off-site commercial firms recycle, reclaim, purify, are used as general depositories of unwanted chemicals and stabilize vacuum pump oil, solvents, mercury, rare become mini-Superfund sites because of lack of control. materials, and metals. Off-site recycling is preferable Academic institutions could recycle common organic to disposal, and sometimes is less expensive. Another solvents from one research laboratory to another, or off-site option is to work with suppliers of laboratory from research laboratories to teaching laboratories. For chemicals who accept return of unopened chemicals, example, chromatography effluents such as toluene including highly reactive chemicals. Gas suppliers could be collected from research laboratories, distilled, sometimes accept returns of partially used cylinders. and checked for purity before reuse. Commercial dis- A general comment applicable to all recycling is that tillation systems are available for such purposes, but a recyclable waste stream needs to be kept as clean as laboratory personnel performing the distillations or possible. If a laboratory produces a large quantity of working in the immediate vicinity need appropriate waste xylene, small quantities of other organic solvents training. (See Chapter 7 for hazards associated with should be collected in a separate container, because the distillation.) distillation process gives a better product with fewer Laboratory-to-laboratory exchange can be an effec- materials to separate. Steps should also be taken to tive alternative to a central surplus-chemical stockroom avoid getting mercury into oils used in vacuum sys- in organizations unwilling or unable to manage a tems, and oil baths. Similarly, certain ions in a solution central storeroom properly. In such a system, trained of waste metal salts have a serious negative impact laboratory personnel retain responsibility for the on the recrystallization process. Identify users for a storage of unwanted chemicals but notify colleagues recycled product before time and energy are wasted periodically of available materials. A chemical track- on producing a product that must still be disposed of ing system as described above facilitates an exchange as a waste. Recycling some of the chemicals used in system greatly. If colleagues within the same laboratory large undergraduate courses is especially cost-effective are using the same hazardous material, particularly one because the users are known well in advance. that is susceptible to decomposition on contact with air Many recycling processes result in some residue that or water, they should try to coordinate the timing of is not reusable and will probably have to be handled as their experiments. a hazardous waste. 5.D.3 Recycling of Chemicals and 5.D.3.2 Solvent Recycling Laboratory Materials Because the choice of a distillation unit for solvent recycling is controlled largely by the level of purity de- 5.D.3.1 General Considerations sired in the solvent, know the intended use of the redis- Chemical recycling takes many forms. In each case a tilled solvent before equipment is purchased. A simple material that is not quite clean enough to be used as is flask, column, and condenser setup may be adequate must be brought to a higher level of purity or changed for a solvent that will be used for crude separations to a different physical state. or for initial glassware cleaning. For a much higher Recycling occurs on-site or off-site. On-site recycling level of purity, a spinning band column is probably occurs at the laboratory or at a central location that required. Stills with automatic controls that shut down collects recyclables from several laboratories. Because the system under conditions such as loss of cooling or on-site recycling can be very time and energy intensive, overheating of the still pot are highly recommended, it may not be economically justifiable. In some cases, because they enhance the safety of the distillation op- although the amount of waste may be quite small, it eration greatly. Overall, distillation is likely to be most can require very expensive disposal if a commercial effective when fairly large quantities (roughly 5 L) of vendor must be used. Before a decision on recycling relatively clean single-solvent waste are accumulated is made, the cost of avoided waste disposal should be before the distillation process is begun. calculated. Because of the difficulty of maintaining the needed level of cleanliness and safety, on-site recycling 5.D.3.3 Recycling Containers, Packaging, and of mercury and other toxic metals is no longer recom- Labware mended. Another significant issue is whether recycling activities require a waste treatment permit under the Laboratory materials other than chemicals, such as Resource Conservation and Recovery Act (RCRA). containers or packaging materials and parts of labora-

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94 PRUDENT PRACTICES IN THE LABORATORY tory instruments, can also be recycled. Examples in- Materials transferred from primary (labeled) bulk clude certain clean glass and plastic containers, drums containers to transfer vessels (e.g., safety cans and and pails, plastic and film scrap, cardboard, office squeeze bottles) should be labeled with chemical paper, lightbulbs, circuit boards, other electronics, and identification and synonyms, precautions, and first-aid metals such as steel and aluminum. Note that an empty information. container may still be subject to management require- Label containers in immediate use, such as beakers ments. See the following regulations: 40 CFR § 261.7 and flasks, with the chemical contents. All reactants (EPA “empty”); 49 CFR § 173.29 (DOT “empty”); 49 should be labeled with enough information to avoid CFR §§ 173.12(c) and 173.28 (DOT “reuse”). confusion between them. 5.D.4 Labeling Commercially Packaged 5.D.6 Labeling Experimental Materials Chemicals Labeling all containers of experimental chemical materials is prudent. Because the properties of an Warning: Do not remove or deface any existing labels on experimental material are generally not completely incoming containers of chemicals and other materials. Commercially packaged (by U.S. manufacturers) known, do not expect its label to provide all necessary chemical containers received from 1986 onward gen- information to ensure safe handling. erally meet current labeling requirements. The label The most important information on the label of an usually includes the name of the chemical and any nec- experimental material is the name of the researcher essary handling and hazard information. Inadequate responsible, as well as any other information, such as labels on older containers should be updated to meet a laboratory notebook reference, that can readily lead current standards. To avoid ambiguity about chemical to what is known about the material. For items that are names, many labels carry the CAS registry number to be stored and retained within a laboratory where the as an unambiguous identifier and this information properties of materials are likely to be well understood, should be added to any label that does not include it. only the sample identification and name are needed. On receipt of a chemical, the manufacturer’s label is (For information about labeling samples for trans- supplemented by the date received and possibly the port and shipping, see section 5.F.) name and location of the individual responsible for purchasing the chemical. If chemicals from commercial 5.D.7 Use of Inventory and Tracking sources are repackaged into transfer vessels, the new Systems in Emergency Planning containers should be labeled with all essential informa- tion on the original container. The most important information to have in an emer- gency is how to access a researcher who is knowledge- able about the chemical(s) involved. In addition, an 5.D.5 Labeling Other Chemical Containers organization’s emergency preparedness plan should The overriding goal of prudent practice in the include what to do in the event of a hazardous material identification of laboratory chemicals is to avoid aban- release. The inventory and tracking systems and the doned containers of unknown materials that may be ability to access and make use of them are essential to expensive or dangerous to dispose of. The contents of proper functioning of the plan in an emergency. The all chemical containers and transfer vessels, including, care taken in labeling chemicals is also extremely im- but not limited to, beakers, flasks, reaction vessels, and portant. (See Chapter 6, section 6.C.10, for a detailed process equipment, should be properly identified. The discussion of what to do in laboratory emergencies.) labels should be understandable to trained laboratory personnel and members of well-trained emergency 5.E STORAGE OF CHEMICALS IN response teams. Labels or tags should be resistant to STOCKROOMS AND LABORATORIES fading from age, chemical exposure, temperature, hu- midity, and sunlight. The storage requirements and limitations for stock- Chemical identification and hazard warning labels rooms and laboratories vary widely depending on on containers used for storing chemicals should in- clude the following information: • level of expertise of the employees, • level of safety features designed into the facility, • identity of the owner, • level of security designed into the facility, • chemical identification and identity of hazard • location of the facility and neighboring homes or component(s), and buildings, • appropriate hazard warnings. • nature of the chemical operations,

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95 MANAGEMENT OF CHEMICALS • accessibility of the stockroom, benches, and emergency equipment areas free of • local and state regulations, stored equipment and materials to allow for ease • insurance requirements, and of egress and access in case of emergency. • building and fire codes. Storing chemicals in stockrooms and laboratories Many local, state, and federal regulations have requires consideration of a number of health and safety specific requirements that affect the handling and stor- factors. In addition to the inventory control and stor- age of chemicals in laboratories and stockrooms. For age area considerations discussed above, proper use of example, radioactive materials, consumable alcohol, containers and equipment is crucial (see section 5.E.3). explosives, dual-use materials, and hazardous waste In addition to the basic storage area guidelines have requirements ranging from locked storage cabi- above, follow these general guidelines when storing nets and controlled access to specified waste containers chemicals: and regulated areas. Stringent requirements may also be placed on an institution by its insurance carriers. • Label all chemical containers appropriately to Controlled substances (e.g., narcotics and other con- ensure that chemicals will be stored safely. trolled prescription drugs) used in research or with • Place the user’s name and the date received on research animals have special requirements. The labo- all purchased materials to facilitate inventory ratory director must first register with the U.S. Drug control. Enforcement Agency (DEA) and with the relevant • To assist in maintaining a clean work environment state agency to purchase, possess, or use a Schedule and to ensure that segregation of incompatible 1–5 controlled substance. Schedule 1 and 2 drugs (e.g., chemicals is maintained, provide a definite stor- morphine, pentobarbital) must be stored in a safe that age place for each chemical and return the chemi- is bolted to the floor or wall. Schedule 3–5 drugs (e.g., cal to that location after each use. chloral hydrate, phenobarbital) must be stored in a • To avoid clutter, avoid storing chemicals on locked drawer or cabinet. Access should be limited to benchtops, except for those chemicals being used the laboratory director and, if necessary, no more than currently. the one or two laboratory members who will be using • To avoid clutter and to maintain adequate airflow, the substance. Detailed inventory records must be kept avoid storing chemicals in chemical hoods, except up-to-date, including amounts purchased, used, left on for those chemicals in current use. hand, and disposed of. Contact your local DEA office • Store volatile toxic or odoriferous chemicals in a for disposal instructions. In some cases a DEA agent ventilated cabinet. Check with the institution’s must witness disposal or packaging for shipment to a environmental health and safety officer. disposal facility. • Provide ventilated storage near laboratory chemi- cal hoods. • If a chemical does not require a ventilated cabinet, 5.E.1 General Considerations store it inside a closable cabinet or on a shelf that In general, store materials and equipment in cabinets has a lip to prevent containers from sliding off in and on shelving designated for such storage: the event of a fire, serious accident, or earthquake. • Do not expose stored chemicals to heat or direct • Avoid storing materials and equipment on top of sunlight. cabinets. With all stored items, maintain a clear- • Observe all precautions regarding the storage of ance of at least 18 inches from the sprinkler heads to incompatible chemicals. allow proper functioning of the sprinkler system • Separate chemicals into compatible groups and [see National Fire Protection Association Standard store alphabetically within compatible groups. 13 (NFPA, 2010)]. See Table 5.1 and Figure 5.1 for one suggested • To make chemicals readily accessible and to re- method for arranging chemicals. Because chemi- duce accidents caused by overreaching, do not cals in storage are contained, their separation by store materials on shelves higher than 5 ft (~1.5 compatibility groups can be simplified. The color- m). If retrieving materials stored above head level, coded system described here allows for ease of use a step stool. storage. As explained in Chapter 6, compatibility • Store heavy materials on lower shelves. While rec- precautions for mixing chemicals are far more ommended for all laboratories, this is particularly complex. important in areas where seismic activity is pos- • Store flammable liquids in approved flammable- sible because items may fall during an earthquake. liquid storage cabinets. • Keep exits, passageways, areas under tables or • Consider the security needs for the materials.

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96 PRUDENT PRACTICES IN THE LABORATORY Examples of Compatible Storage Groups TABLE 5.1 A: Compatible Organic Bases F: Compatible Inorganic Acids not Including Oxidizers or Combustibles Diethylamine Piperidine Hydrochloric acid Triethanolamine Sulfuric acid Benzylamine Phosphoric acid Benzyltrimethylammonium hydroxide Hydrogen fluoride solution B: Compatible Pyrophoric & Water-Reactive Materials J: Poison Compressed Gases Sodium borohydride Sulfur dioxide Benzoyl chloride Hexafluoropropylene Zinc dust Alkyl lithium solutions such as methyl lithium in tetrahydrofuran K: Compatible Explosives or Other Highly Unstable Materials Methanesulfonyl chloride Picric acid dry(<10% H2O) Lithium aluminum hydride Nitroguanidine Tetrazole C: Compatible Inorganic Bases Urea nitrate Sodium hydroxide Ammonium hydroxide L: Nonreactive Flammables and Combustibles, Including Lithium hydroxide Solvents Cesium hydroxide Benzene Methanol D: Compatible Organic Acids Toluene Acetic acid Tetrahydrofuran Citric acid Maleic acid X: Incompatible with ALL Other Storage Groups Propionic acid Picric acid moist (10-40% H2O) Benzoic acid Phosphorus Benzyl azide E: Compatible Oxidizers Including Peroxides Sodium hydrogen sulfide Nitric acid Perchloric acid Sodium hypochlorite Hydrogen peroxide 3-Chloroperoxybenzoic acid NOTE: A larger list of examples can be found on the CD that accompanies this book. SOURCE: Adapted from Stanford University’s Chem Tracker Storage System. Used with permission from Lawrence M. Gibbs, Stanford University. Some chemicals are regulated by federal agencies classification system for the storage of groups of chemi- and require locked cabinets or storage in secure cals by compatibility. The system classifies chemicals areas. into 11 storage groups. Each group should be separated by secondary containment (e.g., plastic trays) or, ide- ally, stored in its own storage cabinet. According to 5.E.2 Storage According to Compatibility this system, it is most important to separate storage It is prudent to store containers of incompatible groups B (compatible pyrophoric and water-reactive chemicals separately. Separation of incompatibles will chemicals) and X (incompatible with all other storage reduce the risk of mixing in case of accidental breakage, groups). These two groups merit their own storage fire, earthquake, or response to a laboratory emergency. cabinets. The accompanying compact disc includes a Even when containers are tightly closed, fugitive va- spreadsheet of hundreds of chemicals listed according pors can cause deleterious incompatibility reactions to these storage groups. that degrade labels, shelves, cabinets, and containers There are other good classification systems for themselves. As discussed in Chapter 4, a far more storing chemicals according to compatibility. At a detailed review of incompatibilities needs to be done minimum, always store fuels away from oxidizers. In when chemicals are deliberately mixed, other systems, the following chemical groups are kept Figure 5.1 (also available on the CD accompanying separate by using secondary containment, cabinets, or this book) and Table 5.1 show an example of a detailed distance:

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97 MANAGEMENT OF CHEMICALS - *Storage Groups J, K, and X: Consult EHS Department. For specific storage, consult manufacturer’s MSDS. FIGURE 5.1 Compatible storage group classification system. This system should be used in conjunction with specific storage conditions taken from the manufacturer’s label and material safety data sheet. SOURCE: Adapted from Stanford University’s ChemTracker Storage System. Used with permission from Lawrence M. Gibbs, Stanford University. NOTE: Also available on the CD accompanying this book. 5.E.3 Containers and Equipment • oxidizers, including peroxides; • corrosives—inorganic bases; Specific guidelines regarding containers and equip- • corrosives—inorganic acids, not including oxidiz- ment to use in storing chemicals are as follows: ers or combustibles; • flammable materials; • Use of corrosion-resistant storage trays as sec- • reproductive toxins; ondary containment for spills, leaks, drips, or • select carcinogens; and weeping is a good idea. Polypropylene trays are • substances with a high degree of acute toxicity. suitable for most purposes. • Use secondary containment (i.e., an overpack) to Depending on the chemicals, their amounts, and retain materials if the primary container breaks the activities of your laboratory, it may make sense to or leaks. separate these alternative storage groups. Also be sure • Provide vented cabinets beneath chemical hoods to follow any storage information on the container’s for storing hazardous materials. (This encour- label or on the chemical’s MSDS. ages the use of the hoods for transferring such In seismically active regions, storage of chemicals re- materials.) quires additional stabilization of shelving and contain- • Seal containers to minimize escape of corrosive, ers. Shelving and other storage units should be secured flammable, or toxic vapors. and contain a front-edge lip to prevent containers from falling. Ideally, containers of liquids are placed on a 5.E.4 Cold Storage metal or plastic tray that could hold the liquid if the container broke while on the shelf. All laboratories, not Safe storage of chemicals, biologicals, and radioac- only those in seismically active regions, benefit from tive materials in refrigerators, cold rooms, or freezers these additional storage precautions. requires good labels, organization, and active manage-

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98 PRUDENT PRACTICES IN THE LABORATORY ment. The laboratory director assigns responsibility • construction of the laboratory, for keeping these units safe, clean, and organized and • number of fire control zones in the building, monitors their proper operation. Extra care is required • floor level where the laboratory is located, because frost and condensation not only obscure labels • fire protection systems built into the laboratory, but also make containers hard to hold and easy to drop. • storage of flammable liquids in flammable-liquid Too often, research materials are stored haphazardly in storage cabinets or safety cans, and cold storage areas. To ensure safety: • type of laboratory (i.e., instructional or research and development). • Use chemical storage refrigerators only for storing chemicals. Many laboratories have a business (B) classification • Use waterproof tape and markers to label labora- with sprinkler systems and a flammable and combus- tory refrigerators and freezers with the following: tible liquid storage limitation, as shown in Table 5.2. Note that laboratory unit fire hazard classes are based on the quantities of flammable and combustible liquids NO FOOD—LAB CHEMICAL STORAGE in the space. This classification significantly affects the ONLY fire separation requirements for the laboratory. Most • Do not store flammable liquids in a refrigera- research laboratories fall under Class B, C, or D. tor unless it is approved for such storage. Such Note that some laboratories may be in jurisdictions refrigerators are designed not to spark inside that refer to the International Code Agency rather than the refrigerator. If refrigerated storage is needed NFPA, and state and local regulations may be more inside a flammable-storage room, it is advisable stringent than those cited here. Laboratory personnel to choose an explosion-proof refrigerator. Do not and organization should be sure to check the require- store oxidizers or highly reactive materials in the ments specific to their area. same unit as flammables. The container size for storing flammable and com- • All containers must be closed and stable to reduce bustible liquids is limited both by NFPA Standards the risk of a spill. Round-bottom flasks need sec- 30 and 45 and by the Occupational Safety and Health ondary containment. Administration (OSHA). Limitations are based on the • Label all materials in the refrigerator with con- type of container and the flammability of the liquid, as tents, owner, date of acquisition or preparation, shown in Table 5.3. and nature of any potential hazard. Label all chemical containers with the identity of the • Organize contents by owner but keep incompat- contents and hazard warning information. All chemical ibles separate. Organize by labeling shelves and waste containers must have appropriate waste labels. posting the organization scheme on the outside of Flammable liquids that are not stored in safety cans the unit. should be placed in storage cabinets rated for flam- • Secondary containment, such as plastic trays, is mable storage. When space allows, store combustible highly recommended for all containers. Second- liquids in flammable-storage cabinets. Otherwise, store ary containment captures spills and leaks and combustible liquids in their original containers. Store facilitates organization and labeling. 55-gal drums of flammable and combustible liquids • Every year, review the entire contents of each cold in special storage rooms for flammable liquids. Keep storage unit. Dispose of all unlabeled, unknown, flammable and combustible liquids away from strong or unwanted materials. oxidizing agents, such as nitric or chromic acid, per- • When any trained laboratory personnel leaves, manganates, chlorates, perchlorates, and peroxides. review the contents of each cold storage unit to Keep flammable and combustible liquids away from identify that person’s material, so that it can be any ignition sources. Remember that many flammable disposed of or reassigned. vapors are heavier than air and can travel to ignition sources. Take the following additional precautions when storing flammable liquids: 5.E.5 Storing Flammable and Combustible Liquids • When possible, store quantities of flammable NFPA Standard 45 (NFPA, 2004) limits the quantity liquids greater than 1 L (approximately 1 qt, or 32 of flammable and combustible liquids in laboratories. oz) in safety cans. Refer to Table 5.3. (International, state, and local building codes and regu- • Store combustible liquids either in their original lations should also be consulted.) The quantity allowed (or other NFPA- and DOT-approved) containers depends on a number of factors, including or in safety cans. Refer to Table 5.3.

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99 MANAGEMENT OF CHEMICALS Storage Limits for Flammable and Combustible Liquids for Laboratories with TABLE 5.2 Sprinkler System (maximum 100 ft2 laboratory space) Excluding Quantities in Rated Including Quantities in Rated Storage Cabinets/Safety Cans Storage Cabinets/Safety Cans Laboratory (max per 100 ft2) (max per 100 ft2) Unit Fire Hazard Class Class of Liquid gal L gal L A Class I flammable 10 38 20 76 (flash point <100 °F) (high fire hazard) Combined Class I, II, IIIA 20 76 40 150 (flash point <200 °F) B Class I flammable 5 20 10 38 (flash point <100 °F) (moderate fire hazard) Combined Class I, II, IIIA 10 38 20 76 (flash point <200 °F) C Class I flammable 2 7.5 4 15 (flash point <100 °F) (low fire hazard) Combined Class I, II, IIIA 4 15 8 30 (flash point <200 °F) D Class I flammable 1 4 2 7.5 (flash point <100 °F) (minimal fire hazard) Combined Class I, II, IIIA 1 4 2 7.5 (flash point <200 °F) NOTE: Limits for laboratories in health care occupancies and in K-12 educational facilities may be significantly lower. SOURCE: Reproduced with permission from NFPA 45, Fire Protection for Laboratories Using Chemicals, Copyright 2004, National Fire Protection Association. This reprinted material is not the complete and official position of NFPA on the referenced subject, which is represented only by the standard in its entirety. Container Size for Storage of Flammable and Combustible Liquids TABLE 5.3 Flammable Liquidsa Combustible Liquidsb Class IA Class IB Class IC Class II Class IIIA Container L gal L gal L gal L gal L gal Glassc,d 0.5 0.12 1 0.25 4 1 4 1 20 5 Metal/approved plasticd 4 1 20 5 20 5 20 5 20 5 Safety cansd 10 2.6 20 5 20 5 20 5 20 5 NOTE: Label safety cans with contents and hazard warning information. Safety cans containing flammable or combustible liquid waste must have appropriate waste labels. Place 20-L (5-gal) and smaller containers of flammable liquids that are not in safety cans in storage cabinets for flammable liquids. Do not vent these cabinets unless they also contain volatile toxics or odoriferous chemicals. Aerosol cans that contain 21% (by volume), or greater, alcohol or petroleum-based liquids are considered Class IA flammables. When space allows, store combustible liquids in storage cabinets for flammable liquids. Otherwise, store combustible liquids in their original (or other Department of Transportation–approved) containers according. Store 55-gal drums of flammable and combustible liquids in special storage rooms for flammable liquids. Keep flammable and combustible liquids away from strong oxidizing agents, such as nitric or chromic acid, permanganates, chlorates, perchlorates, and peroxides. Keep flammable and combustible liquids away from an ignition source. Remember that most flammable vapors are heavier than air and can travel to ignition sources. aClass IA includes those flammable liquids having flash points <73 °F and having a boiling point <100 °F, Class IB includes those having flash points <73 °F and having a boiling point ≥100 °F, and Class IC includes those having flash points ≥73 °F and <100 °F. Aerosol cans that contain 21% (by volume), or greater, alcohol or petroleum-based liquids are considered Class IA flammables. bClass II includes those combustible liquids having flash points at ≥100 °F and <140 °F, Class IIIA includes those having flash points ≥140 °F and <200 °F, and Class IIIB includes those having flash points ≥200 °F. cGlass containers as large as 1 gal can be used if needed and if the required purity would be adversely affected by storage in a metal or approved plastic container, or if the liquid would cause excessive corrosion or degradation of a metal or approved plastic container. dIn educational and institutional laboratory work areas, containers for Class I or Class II liquids should not exceed 8 L (32.1 gal) for safety cans or 4 L (1 gal) for other containers. SOURCE: Reproduced with permission from NFPA 45, Fire Protection for Laboratories Using Chemicals, Copyright© 2004, National Fire Protection Association. This reprinted material is not the complete and official position of NFPA on the referenced subject, which is represented only by the standard in its entirety.

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100 PRUDENT PRACTICES IN THE LABORATORY 5.E.6 Storing Gas Cylinders • Consider the storage requirements of each highly reactive chemical prior to bringing it into the Check applicable international, regional, or local laboratory. building and fire codes to determine the maximum • Consult the MSDSs or other literature in mak- amount of gas to be stored in a laboratory. These limits ing decisions about storage of highly reactive vary by storage conditions and type of chemical. chemicals. With toxic and reactive gases, or large quantities • Bring into the laboratory only the quantities of of asphyxiating gases, a special gas cabinet may be material needed for immediate purposes (<3- to required. Gas cabinets are designed for leak detection, 6-month supply, depending on the nature and safe change-outs, ventilation, and emergency release. sensitivity of the materials). The following general precautions should be taken • Label, date, and inventory all highly reactive when storing compressed gas cylinders or lecture materials as soon as received. Make sure the label bottles: states • Always label cylinders with their contents; do not DANGER! HIGHLY REACTIVE MATERIAL! depend on the manufacturer’s color code. They may vary across companies. • Do not open a container of highly reactive mate- • Securely strap or chain gas cylinders to a wall or rial that is past its expiration date. Call your insti- benchtop. In seismically active areas, use more tution’s hazardous waste coordinator for special than one strap or chain. instructions. • When cylinders are no longer in use, shut the • Do not open a liquid organic peroxide or peroxide valves, relieve the pressure in the gas regulators, former if crystals or a precipitate are present. Call remove the regulators, and cap the cylinders. your institution’s hazardous waste coordinator • Segregate gas cylinder storage from the storage of for special instructions. other chemicals. • For each highly reactive chemical, determine a re- • Do not store corrosives near gas cylinders or lec- view date to reevaluate its need and condition and ture bottles. Corrosive vapors from mineral acids to dispose of (or recycle) material that degrades can deface markings and damage valves. over time. • Keep incompatible classes of gases stored sepa- • Segregate the following materials: rately. Keep flammables away from reactives, oxidizing agents from reducing agents and which include oxidizers and corrosives. (For more combustibles, information on storage of flammable gases, see powerful reducing agents from readily reduc- Chapter 7, section 7.D.3.3.) ible substrates, • Segregate empty cylinders from full cylinders. pyrophoric compounds from flammables, and • Keep in mind the physical state—compressed, perchloric acid from reducing agents. cryogenic, or liquefied—of the gases. • Store highly reactive liquids in trays large enough • Do not abandon cylinders in the dock storage to hold the contents of the bottles. areas. • Store perchloric acid bottles in glass or ceramic • Return cylinders to the supplier when you are trays. finished with them. • Store peroxidizable materials away from heat and light. For commonly used laboratory gases, consider the • Store materials that react vigorously with water installation of in-house gas systems. Such systems away from possible contact with water. remove the need for transport and in-laboratory han- • Store thermally unstable materials in a refrigera- dling of compressed gas cylinders. Chapter 6, section tor. Use a refrigerator with these safety features: 6.H, provides additional information on working with all spark-producing controls on the outside, compressed gases in the laboratory. a magnetically locked door, an alarm to warn when the temperature is too 5.E.7 Storing Highly Reactive Substances high, and a backup power supply. Check applicable international, regional, or local • Store liquid organic peroxides at the lowest pos- building and fire codes to determine the maximum sible temperature consistent with the solubility amount of highly reactive chemicals that can be stored or freezing point. Liquid peroxides are particu- in a laboratory. These limits vary by storage conditions larly sensitive during phase changes. Follow the and type of chemical. Follow these additional guide- manufacturer’s guidelines for storage of these lines when storing highly reactive substances:

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101 MANAGEMENT OF CHEMICALS highly hazardous materials. (See Chapter 4, sec- institution should walk. (Secondary containment, such tion 4.D.) as a rubber bucket, should always be used for carrying • Inspect and test peroxide-forming chemicals peri- bottled chemicals.) Organizations located in a larger odically (these should be labeled with an acquisi- campus setting should have guidelines indicating if tion or expiration date), and dispose of chemicals special courier or designated vehicles are to be used to that have exceeded their safe storage lifetime. transport regulated materials according to applicable • Store particularly sensitive materials or larger regulations. amounts of explosive materials in explosion relief Samples of experimental material to be transferred boxes. outside the laboratory, or that may be handled by indi- • Restrict access to the storage facility. viduals not generally familiar with the type of material • Assign responsibility for the storage facility and involved, should be labeled as completely as possible. the above responsibilities to one primary person In addition, hazardous samples sent to individuals at and a backup person. Review this responsibility another institution must be accompanied by appro- at least yearly. priate labeling and an MSDS, according to OSHA’s Hazard Communication Standard amendments and OSHA’s Laboratory Standard hazard identification 5.E.8 Storing Highly Toxic Substances provision, including the name, address, and contact Take the following precautions when storing carcino- information of the sender and recipient for samples gens, reproductive toxins, and chemicals with a high in transit. When available, the following information degree of acute toxicity: should accompany experimental materials: • Store chemicals known to be highly toxic in venti- • Originator: List the name of the owner or indi- lated storage in unbreakable, chemically resistant vidual who first obtained the material. If send- secondary containment. ing the material to another facility, add contact • Keep quantities at a minimum working level. information for the person who can provide safe • Label storage areas with appropriate warning handling information. signs, such as • Identification: Include, at least, the laboratory notebook reference. • Hazardous components: List primary compo- CAUTION! REPRODUCTIVE TOXIN nents that are known to be hazardous. STORAGE or • Potential hazards: Indicate all known or potential hazards. CAUTION! CANCER-SUSPECT AGENT • Date: Note the date that the material was placed STORAGE in the container and labeled. • Limit access to storage areas. • Ship to: Indicate the name, location, and tele- • Maintain an inventory of all highly toxic chemi- phone number of the person to whom the material cals. Keep records of acquisition, use, possession, is being transferred. and disposal. Some localities require that inven- tories be maintained of all hazardous chemicals in When transporting or shipping most chemicals, bio- laboratories. logical agents, and radioactive materials, even small amounts or samples preserved in solvents or alcohol, Note: Facilities covered by the OSHA Laboratory domestically or internationally, please note that the Standard must use and store carcinogens, reproduc- DOT or the International Air Transport Association tive toxins, and chemicals with a high degree of acute (IATA) regulations may apply. Before preparing any toxicity in designated areas. packages for shipment, personnel must have docu- mented evidence that they have complete DOT and IATA training. DOT controls shipment of chemicals 5.F TRANSFER, TRANSPORT, AND by a specific set of hazardous materials regulations, SHIPMENT OF CHEMICALS 49 CFR Parts 100-199 (updated 2006). These regula- U.S. and international regulations apply to the tions contain detailed instructions on how to identify, movement of chemicals, samples, and other research package, mark, label, document, and placard hazard- materials on public roads, by airplane, or by mail or ous materials. Shipments not in compliance with the other carrier. When moving these materials on-site, applicable regulations may not be offered or accepted anyone personally transporting regulated materials for transportation. The regulations on training for safe between adjacent or neighboring buildings within an transportation of hazardous materials are located in

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102 PRUDENT PRACTICES IN THE LABORATORY 49 CFR § 172.700–172.704 (updated Oct. 1, 2006). All • educational demonstrations (i.e., chemicals for individuals who are preparing hazardous materials for public school outreach education programs). shipment must communicate with their institution’s transportation coordinators. Shipment of experimental Under this exemption, it is permissible to transport materials is also discussed in Chapter 11, sections 11.F.1 your own hazardous materials as long as certain and 11.F.2. conditions are met. These include proper packaging The use of personal vehicles, company or institu- according to DOT requirements. The packaging must tional vehicles (including airplanes), and customer ve- be the manufacturer’s original packaging or a package hicles for transporting regulated materials, which may of equal or greater strength and integrity. The packag- be hazardous, is a major concern. In many cases, han- ing must be marked with a common name or a proper dling regulated materials in this manner is prohibited shipping name from the Hazardous Materials Table. by DOT or will require shipping papers, placarding, Other requirements are and/or other conditions. Most businesses and academic • Packagings must be leaktight for liquids and institutions forbid the use of privately owned personal gases, and siftproof for solids. vehicles, because of the serious insurance consequences if • Packages must be securely closed, secured against an accident occurs. Most individuals will find that their movement, and protected against damage. personal vehicle insurance does not cover them when they • Outer packagings are not required for receptacles are transporting hazardous materials. Shipping chemicals by air is regulated by IATA. An (such as cans or bottles) that are secured against individual who holds IATA certification must inspect movement in cages, bins, boxes, or compartments. the packaging, review the paperwork, and sign the • Cylinders and pressure vessels must conform to shipping papers. For domestic shipping by ground or DOT’s hazardous materials regulations (49 CFR rail, DOT regulations apply and may require a bill of Parts 171–180) except that outer packagings are lading or manifest, placarding, special packaging, and not required. These cylinders must be marked other conditions. with the proper shipping name and identification Be aware that international transfer of chemicals and number and have a hazard class warning label. research materials is regulated by EPA, the Department • If the package contains a reportable quantity of of Commerce, and the U.S. Customs Bureau as imports a hazardous substance, it must be marked “RQ.” and exports. Federal and international laws strictly reg- Reportable quantities are found in Appendix A of ulate domestic and international transport of samples, 49 CFR § 172.101. specimens, drugs, and genetic elements, as well as re- search equipment, technologies, and supplies—even if 5.F.2 Transfer, Transport, and Shipment of the material is not hazardous, valuable, or uncommon. Nanomaterials Mail, shipments, and luggage are being screened for these materials. Packages to or from research institu- This guidance applies to the movement of mate- tions receive additional scrutiny, as well as any package rial from a laboratory to and from off-site locations. that appears to contain bottles or liquids. Personnel who package and prepare nanomaterials Chapter 8 describes the requirements for shipping for shipment off-site must be current on hazardous hazardous waste. material employee training required by 49 CFR Part 172, Subpart H. Consult your institution’s shipping department for assistance and routing of your mate- 5.F.1 Materials of Trade Exemption rials. Although the guidelines provided here are for DOT has an exception to many requirements for nanomaterials, the procedures are worth considering transportation of hazardous materials, referred to as for shipping any material. the “materials of trade” (MOT) exemption, which ap- Any nanomaterial that meets the definition of a plies to the transportation of small quantities of hazard- hazardous material according to 49 CFR § 171.8 and is ous materials that are part of your business. Examples classified as a hazardous material in accordance with include the following: 49 CFR §§ 173.115–173.141 and 173.403–173.436 must be packaged and marked, and labeled shipping papers • facilities maintenance services (i.e., paints and must be prepared. The package must be shipped in ac- p aint thinners for painters and gasoline for cordance with 49 CFR Parts 100–185 and all applicable groundskeepers), regulations. • researchers (i.e., preservatives for field samples), Any nanomaterial shipped by air that meets the and definition of a dangerous good according to the In-

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103 MANAGEMENT OF CHEMICALS ternational Civil Aviation Organization (ICAO) must be packaged, marked, labeled, and shipped with an accompanying properly prepared dangerous goods declaration in accordance with the ICAO technical instructions. Nanomaterials that are suspected to be hazardous (e.g., toxic, reactive, flammable) should be classified, labeled, marked, and manifested as though that haz- ard exists. These materials should be classified and shipped as samples according to 49 CFR § 172.101(c) (11) unless the material is specifically prohibited by sec- tions 173.21, 173.54, 173.56(d), 173.56(e), 173.224(c), or 173.225(b). These suspect materials should be packaged FIGURE 5.2 Recommended inner packaging label for on- in accordance with sections 5.F.2.1 and 5.F.2.2, below. site transfer of nanomaterials. Nanomaterials that do not meet DOT’s criteria listed above may pose health and safety risks to personnel handling the materials if the materials are released dur- ing transport. Therefore, all shipments of nanomateri- Documentation and notifications for off-site transfer als, regardless of whether they meet the definition for of nanomaterials should include the following: hazardous materials, should be consistently packaged using the equivalent of a DOT-certified packing group • a signed and complete dangerous goods declara- I (PG I) container and labeled as described in section tion or shipping papers prepared in accordance 5.F.2.1, below. with ICAO and DOT regulations by certified/ qualified hazardous material employees who are 5.F.2.1 Off-Site Transport and Shipments of authorized to release materials from the site; Nanomaterials • available descriptions of the material (e.g., MSDSs) (researchers should prepare a document for the This section applies to nanomaterials that are sent to samples that describes known properties and a laboratory and from a laboratory to off-site locations other properties that are reasonably likely to be and that do not otherwise meet the DOT definition of exhibited by samples); and hazardous material. • a notification to the receiving facility of the incom- The outer and inner package should meet the defi- ing shipment. nition of PG I–type package. The innermost container should be tightly sealed to prevent leakage of nanoma- All materials should be transported by a qualified terials. It should have a secondary seal, such as a tape carrier. seal, or a wire tie to prevent a removable closure from inadvertently opening during transport. • Shipments of nanomaterials classified as other The outer package should be filled with shock- materials (neither recognized HazMat or sus- absorbing material that can pected DOT HazMat) may be transported using the most expeditious method provided they are • protect the inner sample container(s) from dam- packaged according to the requirements in sec- age and tion 5.F.1. • absorb liquids that might leak from the inner • The driver must possess basic hazard information container(s) during normal events in transport. on the commodity being transported, that is, ma- terial name, quantity, form, and MSDS if available. As depicted in Figure 5.2, the inner package should be labeled (not to be confused with DOT hazard labeling). 5.F.2.2 On-Site Transfer and Transport of If the nanomaterial is in the form of dry dispersible Nanomaterials particles, add the following line of text: The on-site transfer of nanomaterials should follow the site-specific transportation safety document or Nanomaterials can exhibit unusual reactivity other institutional document (i.e., Chemical Hygiene and toxicity. Avoid breathing dust, ingestion, Plan); in lieu of such a document, the transfer should and skin contact.

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104 PRUDENT PRACTICES IN THE LABORATORY fully comply with DOT requirements. The site’s trans- • Mark the transfer containers in accordance with portation authority (e.g., transportation safety officer the recommendations for off-site shipments. or equivalent) should be the authority having jurisdic- • Include the following documents in the package: tion over the requirements for packaging, marking, o results of the safety assessment and and documenting necessary for on-site transfers. For o an MSDS, if available, or a similar form de- nanomaterials, the following is suggested: tailing possible hazards associated with the material. • A ssess and record the hazards posed by the • N otify the receiving facility of the incoming material(s) following a graded approach that shipment. takes into account the form of the material(s) (e.g., free particle versus fixed on substrate). • Use packaging consistent with the recommen- dations for off-site shipment or that affords an equivalent level of safety.