LESS IS BETTER Introduction Chemicals that have no further use are waste chemicals and must be disposed of properly. In a laboratory, these wastes can include reaction products as well as unwanted chemicals. An objective of the American Chemical Society (ACS) is to promote alternatives to landfilling for the disposal of laboratory chemical wastes. One method is to reduce the amount of chemicals that may become wastes. This approach differs from other practices in that it is rooted in the philosophy that "less is better." The "less is better" concept depends on the establishment of a comprehensive chemical management system. Through such an approach, all the sources of potential waste generation are identified and are managed to reduce the amount of hazardous chemical wastes produced in laboratory operations. Other advantages of this system include conserving resources and minimizing the potential harm to personnel in the event of an accident. Some waste chemicals are legally declared and classified as hazardous under government regulations. Many additional chemicals, if improperly handled, may be hazardous because of their potential for harm. Generators of any quantity of hazardous chemical wastes have a legal as well as an ethical obligation to dispose of these wastes in such a manner so as no risk is posed to the public or the environment. Thus, federally-designated hazardous wastes must be carefully collected, separated, packaged, labeled, recorded, and disposed of in strict accordance with prescribed regulations. Not all chemicals, however have a potential for harm - they are classed as non- hazardous. Some non-hazardous materials may be safely and legally disposed of through the sewer system or as vapors in a hood and ventilating system. Other non- hazardous substances may be removed by the sanitary trash collector. Some wastes are incinerated while others like solvents may be purified and reused. Because of the diversity of the wastes generated in laboratories, prudent disposal of these chemicals demands considerable expertise and attention. This bulletin discusses the various techniques that can be employed to develop a "less is better" philosophy of hazardous waste management, as well as the practical benefits that can be gained from implementing such a program. It is intended for those persons responsible for managing laboratory hazardous waste chemicals in industry, academe, and elsewhere: chemists at the bench, professors and science teachers, research directors and laboratory managers, stockroom managers, business managers, purchasing agents, and safety personnel. The bulletin is composed of five sections that address waste reduction through management techniques such as purchasing control, inventory control, surplus chemical exchange, reclamation, and recycling. The fifth section presents practical examples of minimizing waste through careful and comprehensive planning in teaching and research laboratories. The Impact of Purchasing Strategy The chemicals used in laboratories are usually less costly than the associated labor and equipment required to manage them. As a matter of convenience, chemicals are frequently purchased in only one package size, often in large quantities. The user selects the size and often will opt for the maximum reasonable quantity with the lowest unit purchase price. Subsequent storage of chemicals in excess of short term need may seem to have a monetary advantage. However rising storeroom expenses and associated disposal costs are changing that assumption. Liabilities associated with the risks to safety and health from unplanned chemical exposure to stored chemicals also contribute to the escalation of laboratory operating costs. When a quantity of a chemical is used from a small or large container the unused remainder of the substance (that is, the excess chemical) is retained. Many experimenters prefer to begin a new procedure or each new phase of an experiment with fresh material dispensed from unopened, original containers. Partially-filled containers thus accumulate in the laboratories and storerooms. These excess chemicals are often disposed of at the conclusion of a project, when another scientist takes over the laboratory or when the laboratory is refurbished for a new use. Unused chemicals can constitute as much as 40% of the hazardous waste generated from laboratories. This waste consists of chemicals still in their original containers which have outlived or appear to have outlived their usefulness due to partial degradation over time or from a judgment being made that the chemical will not be used in the future. Excess quantities of such chemicals are found in the storerooms, on laboratory shelves, under benches, in hoods, and in various other places. The surplus from large containers places increased demands, in terms of expense, time, and workforce, on the waste removal function. By contrast, when chemicals are drawn from the storeroom in small packages, less material circulates throughout the organization and smaller amounts ultimately require disposal. The inventoried package size is, therefore, critical for minimizing waste. If for example, 300 ml of material is dispensed from a 500 ml container, frequently the balance of 200 ml is disposed of. When 300 ml is taken from a 1000 ml or larger container the 700 ml balance may remain stored on the laboratory shelf for many years. Most of the remaining chemical is never used in another laboratory procedure. This translates into higher costs for the materials actually used and into additional costs for disposal of the unused portions. Extended storage of unused chemicals increases the risk of accidents. Smaller quantity purchases result in less unused chemicals being stored and reduce the potential for chemical exposure to personnel. Smaller bottles tend to break less often than larger ones. If they do break, spillage is less and cleanup is easier and safer. Personnel safety reasons alone justify limited inventories of smaller packages. Purchasing-Disposal Economics The real cost of a chemical includes its initial purchase price plus the ultimate disposal costs. From the viewpoint of purchasing, the quantity actually used relative to the quantity purchased governs the unit purchasing cost. The perceived economy of purchasing chemicals in large quantity containers may be deceptive. Consider phenol in an example of purchasing a large "economical size" package rather than in a smaller size container or containers more consistent with the immediate need. We will assume that the same quantity of phenol will be used in either case and that any remaining chemical will be disposed of. Phenol is available in 500 ml bottles at a cost (in 1984 dollars) of $15.50 per bottle or in 2500 ml bottles at a cost of $52.00. If 1000 ml are used in either of the purchasing examples, the cost of phenol used is 3.1 cents/ml and 5.2 cents/ml, respectively. Large container purchases are only economical if a significant portion of the chemical is actually used. In this example, 1677 ml from the larger bottle must be used before the cost per ml comes down to the 3.1 cents cost per ml of purchase in the smaller bottles. Now consider the disposal costs for the excess unused material from either of the containers. From the viewpoint of disposal economics, our example, reagent phenol, is classified by EPA as a toxic organic. Phenol is corrosive and flammable. If ingested, it is a severe health hazard; on skin contact it is toxic by absorption. If it gets into a drinking water source, chlorination in a water-treatment plant will convert it to bad tasting chlorophenols. Because of these characteristics, liquid phenol requires costly preparation by waste disposal experts before it can be discarded. Hazardous wastes, such as phenol, are accumulated, stored, packaged, labeled, and disposed of in accordance with specific federal and state regulations. A "lab pack" is the usual package of choice for laboratory waste disposal. A lab pack is a DOT specified 17H metal drum of 55 gallon capacity that is filled with waste materials in their purchased or stored packages. Regulations require that inert packing material be used to surround each inside package in order to separate and maintain the integrity of the small bottles and cans containing the wastes. Packing material must be sufficient to absorb any liquid released from broken or leaking internal packages. The maximum liquid volume of waste contained in the lab pack will be about 15 gallons. The cost (in 1984 dollars) of a filled lab pack, including its preparation, packaging, labeling, transport, and disposal in a secure landfill averages $340 ($23 per gallon of contained waste based on the 15-gallon maximum capacity). Some waste haulers will decline to pick up a single lab pack and some have a minimum charge that is equivalent to a two- or four-drum price. Partially filled containers occupy as much space in the lab pack as do full containers of the same maximum volume. Therefore, the most cost-effective lab pack is that which contains the largest number of filled containers. However because of safety precautions, disposal services that prepare lab packs will not normally dispense or pour waste from one package into another to fill up a container. A lab pack, properly prepared, will accommodate about 52 500-ml bottles. At a cost of $340 for the lab pack, 500 ml bottles cost $6.54 each, no matter how much waste they contain. A 2500 ml bottle is worth $22.57 in lab pack space. Assume that we have used 1000 ml of phenol for our experiment. Two 500 ml bottles will be empty and, if properly rinsed into the reaction vessel, will be clean, and not require disposal. The unit total cost of phenol used from these bottles will only be the purchase price of 3.1 cents/ml. The 1000 ml of phenol used from the 2500 ml bottle cost $52.00 and if it is disposed of with (or without) the remaining liquid, will cost another $22.67 for disposal. The total purchase-disposal cost for the 1000 ml of phenol from the 2500 ml bottle is $74.67, making the unit total cost 7.5 cents/ml used. Even if the breakeven purchase volume of 1677 ml is taken into account, the larger cost for disposal of the 2500 ml bottle with some remaining phenol makes the total cost greater than using 1677 ml from four 500 ml bottles. When using the smaller size containers, three empty bottles will be cleaned and only the one, still partially-filled 500 ml bottle will be disposed of. In this last comparison the unit total costs per ml used is 4.1 cents and 4.5 cents respectively This illustration demonstrates that the favorable purchase price of the larger package can quickly be offset by the disposal costs for that package and its residues. The phenol example also shows the significant and sometimes unrecognized costs associated with the disposal aspect of hazardous chemical usage. The purchase of many small containers rather than one large container may be the most cost-effective and safest way to acquire laboratory chemicals. Phenol represents one laboratory chemical that currently can be disposed of in a landfill using a lab pack. However certain kinds of chemical wastes such as peroxides, reactive metals, and explosives cannot be disposed of in lab packs. Disposal costs for these wastes are usually considerably higher than those for lab packs. For example, at one institution, 20 one-pound bottles of picric acid were disposed of by detonation by a commercial waste disposal firm. The cost (1982) was $160 per bottle; a total of $3200. The price of picric acid at that time was $16 per one pound bottle. Using these economic illustrations, an examination of the purchase, storage, use, and disposal cycle reveals that standardization of the smaller package size of chemicals for laboratory use makes good management sense. Inventory Control A comprehensive chemical management system makes efficient use of purchasing strategy with minimal interference to teaching and research functions. It requires information about the kinds, quantities, location, and status of all the chemicals within a particular laboratory or facility. Tracking a chemical from purchase and receipt to disposal, in effect, may benefit the institution by reducing the possibility of duplicate purchases. Careful inventory control also minimizes the waste generated from old, partially-used containers of chemicals that age on laboratory shelves, and reduces the chance for accidents. A comprehensive approach to chemical management requires substantial information and a modern file or data system. Some laboratories have instituted data networks and others are establishing such operations, each appropriate for and tailored to the needs and resources of the respective laboratory. For example, a data system linked to bar code labeling has proven to be successful at some facilities. Each chemical container has a bar code identification number plus a unique number to identify a particular container. The chemical is followed through the system using bar code readers within the facility. This allows simple tracking of each particular material. The inventory is readily accessed by laboratory workers who use the chemical formula, chemical name, or trade name, and check the inventory by location or "owner" name. The choice of a coding sequence is an important consideration in this particular type of inventory system. Bar code "system 39" is advocated by the U.S. Government's Department of Defense, end might be a logical "universal" code for laboratory chemicals (and apparatus). Chemical Abstracts registry numbers are universally accepted for identifying specific chemicals. Additional coding might be desirable for manufacturer identification, dating, and reference to chemical safety data. The Scientific Apparatus Makers Association, in conjunction with chemical manufacturers and hospital suppliers, developed a common basis for coding which was made available to the scientific community through the Health Industry Bar Code Council early in 1984. A computer-based inventory system is another example of a comprehensive data network for chemical management. One industrial company uses such a system to operate a central storeroom from which chemicals are taken as needed and any excess is returned for use by others. A significant savings again is realized by reducing inventory and storage and by minimizing surplus chemicals that become waste. The success of this system depends on quality control and rapid supply of the required materials by the central storeroom to the laboratory worker as well as the full cooperation of all laboratory personnel. Inventory systems offer the possibility of linking the search for a chemical with electronic ordering when the desired material is not found on site. Most major chemical suppliers provide electronic access to their catalogs. Ready access to safety information might also be introduced into the system for helping in an emergency or aiding in compliance with OSHA "Hazard Communication" standards or state "Right- To-Know" laws. A readily available inventory listing is a requirement for the sharing of surplus chemicals (see next section). Most laboratories store unwanted chemicals in some facility separate from the main, new chemicals store. room. These materials-including non-commercial research and development products-can become a disposer's nightmare as they age. Frequently they have less than adequate labeling, yet they are often just what the research chemist needs for a special project. An inventory control would allow ready access to these materials and, thus, avoid unnecessary purchasing. A record of materials that must be disposed of as wastes can be enlightening. For example, an indication that the management strategy is worthy of reevaluation is a record showing that significant quantities of a particular chemical are being regularly discarded by a project. The record also might show that various quantities of a single chemical are being discarded among many different projects. Combined purchases and inhouse distribution could provide considerable cost savings on such a chemical. Many laboratory workers may be surprised to learn how their materials fit into the total chemical management scheme of their organization and, thus, they can become more conscientious of purchasing efficiency and minimizing waste generation. The systems described may be beyond the current resources of many academic and small industrial laboratories. The systems do provide working models, however that can be adapted to the resources available for each facility In some cases an elaborate inventory can be accommodated by access to a central main frame computer. A smaller data system accessed by a microcomputer or even a card file system may be appropriate, sufficient, and economically feasible for the chemical inventories of smaller laboratories. The effectiveness of any inventory system, whether it involves a sophisticated computer data base or simple handwritten cards, depends on the cooperation of those using it. No one system is best. Each organization must decide what works best for it and how to gain effective support of the laboratory personnel using the system. Surplus Chemical Exchange; Recycling Many of the materials now treated as waste are actually surplus quantities of perfectly good chemicals. Both opened and unopened containers of these chemicals can accumulate in laboratories. With containers that have been previously opened, some uncertainty may exist regarding the chemicals' purity. However often a high degree of purity is not required for certain reactions and uses, and many potential users would be quite willing to accept opened containers of appropriate chemicals. These chemicals should be exchanged rather than left as a waste. Through a surplus chemical exchange, these materials become part of the inventory of the entire chemical management system. Both active and passive chemical exchanges currently exist. In a passive surplus exchange, brochures listing available chemicals are made available to potential users. Interested parties then direct inquiries to the central exchange which relays this information to the person in possession of the substance. Any subsequent negotiations are left to the two parties involved. To date, most passive chemical exchanges have concentrated on the exchange of relatively large quantities of surplus industrial chemicals. In a number of cases, however laboratory chemicals hove effectively been exchanged within a facility An active exchange, on the other hand, involves an intermediary who brings together the originator and the potential user. This is usually done for a fee and the intermediary may actually take possession of the materials. Such an exchange requires time and effort and can prove to be very effective because of the greater variety and quantity of chemicals made available to potential users. The most effective surplus chemical exchange programs have proven to be in house operations. Since the history of a particular chemical is usually easy to obtain from colleagues, the passive exchange operation is the most common. Such exchanges have been developed in a number of relatively large industrial and university laboratories. The computerized programs that were described in the previous section contribute greatly to exchange programs by providing centralized information on the quantity and types of chemicals available in the laboratories. Some manufacturers or suppliers will accept unopened containers of surplus chemicals within limited periods of time after the date of purchase. This practice, however, does not necessarily solve the overall problem of waste disposal or contribute to waste reduction. The manufacturer also may hove to dispose of the materials if the costs of handling and purifying the materials exceed the value of the chemical in question. Laboratory chemicals that have been used in experiments cannot be considered surplus chemicals. Often they must be purified for further use. Legal liability and the need for quality control require that the use of recycled chemicals normally be restricted to in- house use. When recycling is appropriate, it should be encouraged within the chemical management system. For example, noble metals such as mercury and silver are commonly reclaimed because of their value. Laboratory redistillation of solvents is a practice increasingly used by cost-conscious laboratories. Under certain conditions, the recycling or reclamation of laboratory solvents can be a worthwhile waste reduction method. It must be recognized that most laboratories do not generate enough solvents to warrant the on-site transportation and reprocessing costs associated with commercial solvent recyclers. The economics of these factors demand large quantities to justify on-site handling. The only viable recycling of solvents from laboratories involves redistillation in-house. Small stills are readily available for this reprocessing; the problems that must be addressed are those of labor costs and collection procedures. Because of the low labor costs available from students, recycling is perhaps most practical in an academic laboratory In any laboratory, a commitment must be made to establish and enforce collection procedures. While such reclamation is effective within a laboratory for reuse of its own reagents other uses also are possible. A teaching laboratory for example, may be able to redistill and use toluene that is collected from a number of research laboratories. Other reclaimed materials such as spent acids and solvents may be used in routine maintenance of buildings. Waste Reduction In the Laboratory The safe handling and use of chemicals and their potential environmental impact upon disposal must be a major consideration for all laboratories-industrial as well as academic. One common sense approach to reducing the risks posed by exposure to the hazards of the laboratory wastes that are inevitably produced is to minimize the use of hazardous materials. For example some spent glassware cleaning solutions are hazardous waste after use. Chromic acid solution is corrosive (sulfuric acid) as well as toxic (hexavalent chromium) and requires special care in disposal. Also, alcoholic potassium hydroxide solution is flammable and corrosive. These properties make caution necessary when packaging for disposal and when selecting a disposal option. Though such materials are effective for their intended purpose, they present hazard problems from the standpoint of both safety and disposal. These types of cleaning baths add to a laboratory's hazardous waste stream and should be replaced by one of several proprietary laboratory detergents which usually are highly effective when used properly. Some academic laboratory procedures still specify benzene or carbon tetrachloride as reagents or solvents. These compounds often can be replaced by less hazardous materials. This results not only in safer procedures, but also in wastes that may be be hazardous in some respects. The same is true of other commonly-used hazardous materials. For example, in the standard qualitative test for halide ions, cyclohexane and carbon tetrachloride are equally effective for extracting the halogen. If cyclohexane is used instead of the traditional carbon tetrachloride, the organic layer of the extract is less hazardous and is more readily disposed. Qualitative analysis schemes for heavy metals have been developed that replace sulfide ion by hydroxide ion as a central reagent. Both the reagent and the precipitated (waste) product are significantly less hazardous. In some organic syntheses, hypochlorite ion can replace chromate ion or other oxidizers, thereby avoiding the problems of disposing of the hazardous waste that contains chromium (VI) and other hazardous materials. In a physical chemistry laboratory, less hazardous materials can be used for experiments. For example, in the measurement of vapor pressure-temperature relationships by isotensiscope, isopropyl alcohol is as suitable as carbon tetrachloride. Determination of molecular weight by freezing point lowering methods have often used benzene, a classified carcinogen, as the solvent. In such measurements, cyclohexane works about as well as benzene and the cooling curves seem no more difficult to interpret than those using benzene. In the analytical laboratory numerous options are available to chemists who wish to reduce the quantities of hazardous wastes generated. Extraction solvents can be selected so as to minimize hazards and increase recoverability. Sample sizes can be reduced, thus reducing the quantities of extraction solvents and/or derivatization reagents. In a recent case, a laboratory was extracting a 500 cc of highly contaminated sludge with 500 cc of solvents. The laboratory was able to reduce the sample and extraction solvent volumes to 100 cc each while maintaining the desired detection limits. This reduction affected two waste streams in the laboratory - waste hazardous sample material and waste solvent. When the use of hazardous materials cannot be avoided, many experiments still can be carried out on a very small scale, thereby limiting the quantity of hazardous waste produced. Such minor microscale experiments developed for safety purposes have the added advantage of teaching good laboratory techniques. Small-scale syntheses and analyses not only involve the use of smaller quantities of reagents but they also result in smaller quantities of waste-filter cakes, filter papers, filtrate from washings, and distillation residues. Sometimes it is possible simply to evaporate filtrates, washings. or other liquid residues from small.scale reactions to further reduce the amount of potentially hazardous waste. Another advantage of small-scale reactions is the fact that the glassware used is not as easily broken as is larger scale glassware. Broken glassware that are contaminated with hazardous materials are themselves hazardous wastes. Many analytical procedures involve hazardous reagents and products that result in hazardous waste. HPLC, for example, can result in significant quantities or waste solvents. To minimize the hazardous waste problem in such operations, the specific solvent to be used and the utility of recycling it must be carefully considered. Even when syntheses must be done on a moderately large scale, the identity and purity of the products formed can be verified on a semimicro or microanalytic scale using GLC, HPLC, GC/MS, NMR, spot plates, and chemical microscopy. Many organic and inorganic synthesis procedures have been successfully designed so that the product of one synthesis is the starting material for the next. Chains of from two to five or six steps have thus been designed with a good variety of syntheses. When each step is complete, characterizing measurements are made on a few milligrams of material. The rest goes back into the process so that no product from the earlier steps is left to be disposed of or to be stored. Even in such sequences, however there may be filtrates, filter cakes, still bottoms, and the like to be disposed of. With judicious planning, the volume of such hazardous materials can be reduced to a minimum. Hazardous waste can often be eliminated or minimized by simple in-house reagents or use of smaller-scale procedures. Such treatments should be incorporated and described within normal laboratory procedures, either in laboratory manuals or in the experimental sections of procedures published in the research literature. Waste prevention and minimization are as consequential to economics as they are to environmental protection and human health and safety. They also are particularly important aspects of education. Emphasizing safety considerations to students is a clear responsibility of instructors at all levels of education. Each chemical management scheme-both industrial and academic- is only as good as the conscientious people using it. The successful systems that have waste prevention and reduction as goals often are those that are supported at the highest management levels. To achieve these goals, reduction, elimination, and treatment of hazardous waste have become an essential part of laboratory work. In these situations, "less is better" is not simply a concept to be understood or an afterthought applied to planning. Rather "less is better" is the norm, and cost savings, as well as protection of human health and the environment are the benefits.