United States Environmental Protection Agency Hazardous Waste Engineering Research Laboratory Cincinnati OH 45268 Research and Development EPA/540/S2-86/001 Dec. 1 986 &EPA Project Summary Handbook for Stabilization/ Solidification of Hazardous Waste M. John Cullinane, Jr., Larry W. Jones, Philip G. Malone, Philip A. Spooner, and Terry M. Bliss In response to the growing interest in stabilization and solidification of haz- ardous wastes and contaminated soils and sediments, the Land Pollution Con- trol Division of EPA's Hazardous Waste Engineering Research Laboratory has produced a technical Handbook on the subject. This Handbook provides de- tails of the materials and equipment in common use and outlines methodolo- gies for applying these techniques to hazardous waste problems. Among the subjects covered are waste and site characterization, laboratory testing and leaching protocols, bench and pilot scale testing, and full scale operations. Four stabilization/solidification scenar- ios are presented to illustrate advan- tages, disadvantages, and costs for dif- ferent mixing techniques. This Project Summary was devel- oped by EPA's Hazardous Waste Engi- neering Research Laboratory, Cincin- nati, OH, to announce key findings of the research project that is fully docu- mented in a separate report of the same title (see Project Report ordering infor- mation at back). Introduction The terminology associated with sta- bilization/solidification technology is not rigidly defined and is often confus- ing. For this Handbook, stabilization refers to those techniques that reduce the hazard potential of a waste by con- verting the contaminants into their least soluble, mobile, or toxic form. The physical nature and handling character- istics of the waste are not necessarily changed by stabilization. Solidification refers to techniques that encapsulate the waste in a monolithic solid of high structural integrity. The encapsulation may be of fine waste particles (microen- capsulation) or of a large block or con- tainer of wastes (macroencapsulation). Solidification does not necessarily in- volve chemical interaction between the waste and the solidifying reagents, but may involve mechanically binding the waste into the monolith. Contaminant migration is restricted by vastly de- creasing the surface area exposed to leaching, or by isolating the waste within an impervious capsule. Considerable impetus has been given to stabilization/solidification by both the Resource Conservation and Recovery Act (RCRA) and by the Comprehensive Environmental Response, Compensa- tion and Liability Act (CERCLA). These techniques are often the basis for delist- ing petitions under RCRA, and can be employed to satisfy the prohibition on the landfilling of liquids. Under CERCLA, solidification and encapsula- tion are specifically cited in the NCR (40 CFR 300) as methods to be considered during the feasibility study for remedy- ing releases from contaminated soils and sediments. Stabilization/Solidification Techniques Most stabilization/solidification sys- tems being marketed are proprietary processes involving the addition of ab- sorbents and solidifying agents to a waste. Often the marketed process is changed to accommodate specific types of wastes. Since it is not possible to dis- cuss completely all potential modifica- tions to a process, discussions of most ------- processes are related directly to generic process types. The exact degree of per- formance observed in a specific system may vary widely from its generic type, but the general characteristics of a proc- ess and its products can be discussed. Waste stabilization/solidification sys- tems that have potentially useful appli- cation in remedial action include: • Sorption • Lime-fly ash pozzolan processes • Pozzolan-portland cement processes • Thermoplastic microencapsulation • Macroencapsulation Other less common techniques include: • Self-cementation • Vitrification Pretreatment systems, which overlap with stabilization and sorption proc- esses, can be used to achieve a number of results that condition the waste to en- sure better and more economical con- tainment after the remaining materials have been stabilized and solidified. These include: • Destruction of materials (such as acids or oxidizers) that can react with solidification reagents (lime or port- land cement) • Chemical binding of specific waste constituents to solid phases added to scavenge toxic materials from solu- tion and hold them in solids • Techniques for improving the scale on which waste processing can be done, for example bulking and ho- mogenizing waste to allow a single solidification system to be used with modification on a large volume of waste. Neutralization, oxidation or reduc- tion, and chemical scavenging stabilize the waste, in that they bring the chemi- cal waste into an inert or less soluble form. Dewatering, consolidation, and waste-to-waste blending are also useful pretreatment methods which reduce the waste volume or numbers of differ- ent waste forms requiring treatment. Waste Characterization A thorough physical and chemical characterization of a waste is essential to determining the most suitable stabi- lization/solidification method, as well as any special pretreatment or material handling methods that may be re- quired. Physical characterization fo- cuses mainly on transport, storage, and mixing considerations. Chemical char- acterization focuses mainly on interfer- ing compounds, hazard assessment, and compatibility. Tests performed to characterize the physical properties of a waste will vary with the specific wastes and the stabi- lization/solidification techniques pro- posed for them. The physical determi- nations most commonly employed for stabilization/solidification are: • Moisture content • Suspended solids content • Bulk Density • Grain size distribution • Atterberg limits • Cone index • Unconfined compressive strength The purposes of chemical characteri- zation are to determine the hazards as- sociated with waste handling, to deter- mine if interfering materials are present, and to examine waste/waste and waste/process compatibilities. The hazard potential, used to develop worker health and safety plans and equipment requirements, may be deter- mined by analysis for priority pollu- tants. Tests to determine the presence of compounds deleterious to the in- tended stabilization/solidification proc- ess may be used to identify necessary pretreatment measures. Compatibility testing is used to determine if wastes can be mixed into larger bulks for treat- ment, and to determine if the wastes are amenable to various stabilization/solidi- fication techniques. Process Selection The first measure taken in determin- ing the feasibility of a stabilization/solid- ification technique as a remedial alter- native, is to complete a thorough characterization of the wastes, and to calculate their volume. From this a de- termination of the need to pretreat the wastes can be made. Flammable, corro- sive, reactive, and infectious wastes are among those that should not be consid- ered for solidification without some form of pretreatment. If more than one pretreatment measure is required, as may be the case with complex wastes, some method other than solidification may become more cost-effective. Another use for the waste characteri- zation is to assess the degree of hazard associated with handling the wastes. The equipment and time needed to pro- tect workers and nearby residents while extremely hazardous wastes are being processed may become prohibitively expensive. An additional process selection meas- ure is to characterize the site where the solidified wastes will be disposed. Be- cause all solidification techniques result in increased volumes for disposal, ano transportation costs are significant, wastes are usually solidified at the site where they will be disposed. Conse- quently, wastes are either excavated and hauled to a suitable site or the exist- ing site is made suitable through modi- fications. Many uncontrolled sites can be made suitable to accept solidified wastes through the installation of a liner, leachate collection system, or other engineering measure. As with the costs of pretreatment processes, the costs of site modifications for secure re- burial may become limiting. Another step in selecting a suitable process is to develop the specifications the solidified wastes must meet. Such specifications should include: • Leachability • Free liquid content • Physical stability and strength • Reactivity • Ignitability • Resistance to biodegradation • Permeability Standards for testing stabilized/solidi- fied wastes have not yet been devel- oped. A suggested program of specifi- cation and testing procedures arr outlined in the Handbook. Process Screening Assuming that one or more stabiliza- tion/solidification processes are identi- fied as feasible by the selection proce- dures, bench-scale or pilot scale studies can be used to choose and refine the most suitable technique. Areas of con- cern investigated by these studies in- clude: • Safe waste handling procedures • Waste uniformity • Mixing and pumping properties • Processing parameters • Process control procedures • Volume increases A large stabilization/solidification op- eration has the potential to present many safety concerns. Heat generation, volatilization, and dust propagation are among the potential hazards. Also, the rapid addition of a reactive pretreat- ment or solidification agent such as lime, could cause a flash fire by rapid volatilization of organic chemicals. Many solidification reactions are exothermic, and an evaluation of the heat transfer characteristics of the treat- ment system is essential. The effects of heat transfer on reaction rates as th, system is scaled up must also be evalu ated. ------- Waste uniformity, and the mixing and pumping qualities at various points within the treatment system should also be subject to study. Serious problems can be caused by rapid viscosity in- creases within the system and must be evaluated, along with performance evaluations of the pumps, mixers or other equipment to be used. Process parameters, including mix ra- tios, mix and set times, and volume in- creases are among the most important results of bench or pilot-scale testing. Due to the heterogeneity of wastes and many common treatment materials, many of the process parameters will be determined by trial and error. Moisture content of wastes or treatment agents can show wide variability, and signifi- cantly alter mix ratios. Process Operation Full-scale operation of a solidification process requires detailed planning and cost comparisons. The first planning step involves the characterization, test- ing and process selection efforts de- scribed above. The second phase of planning involves the development of *he operation plan, including equip- lent requirements, work sequence and scheduling, and cost estimation for the specific site. These are briefly discussed below. Equipment requirements are largely determined by the type of mixing to be employed in the process. The four types of mixing commonly used are in-drum, in-situ, plant and area. Project sequencing and scheduling are largely determined by the type of mixing technique employed. The first step generally involves preparation of the site and construction of any neces- sary facilities. These could include exca- vation of an inground mixing pit, or con- struction of a disposal site to receive the processed waste. This is often followed by any needed evaluation of the wastes including such things as drum integrity or phase separations. The actual proc- essing of the wastes then takes place, along with the process control monitor- ing. This is followed by waste curing and final disposal. Variations to these sequences are likely, due to process and site-specific factors. Cost estimations for a full-scale proc- essing operation must take into account costs for: Treatment reagents - Labor • Materials • Equipment • Cleanup • Overhead and profit These will depend on the solidification technique employed, the amount of waste to be processed, and many other site-specific constraints. The number of waste processing, handling, and mixing technologies is highly varied, as is the number of treat- ment reagent-waste formulations. Waste and site characteristics, and reagent cost and availability are the major factors which must be weighted in project planning to ascertain the most cost-efficient and reliable containment strategy. The full report was submitted in par- tial fulfillment of Interagency Agree- ment No. AD-96-F-2-A145 by the U.S. Army Engineer Waterways Experiment Station under the sponsorship of the U.S. Environmental Protection Agency. M. John Cullinane, Jr., Larry W. Jones, and Philip G. Ma/one are with the U.S. Army Engineer Waterways Experiment Station, Vicksburg, MS 39180; the EPA author Terry M. Bliss is with the Hazardous Waste Engineering Research Laboratory, Cincinnati, OH 45268. Janet M. Houthoofd is the EPA Project Officer (see below). The complete report, entitled "Handbook for Stabilization/Solidification of Hazardous Waste," (Order No. PB 87-116 745/AS; Cost: $18.95, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Hazardous Waste Engineering Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G 35 Official Business Penalty for Private Use S300 EPA/540/S2-86/001 ------- |