United States Environmental Protection" Agency Office of Emergency and Remedial Response Washington, DC 20460 Office of Research and Development Cincinnati, OH 45268 Superfund EPA/540/S-97/500 August 1997 <&EFA Engineering Bulletin Technology Alternatives for the Remediation of Soils Contaminated with As, Cd, Cr, Hg, and Pb Purpose Section 121(b) of the Comprehensive Environmental Re- sponse, Compensation, and Liability Act (CERCLA) mandates the U.S. Environmental Protection Agency (EPA) to select rem- edies that "utilize permanent solutions and alternative treatment technologies or resource recovery technologies to the maximum extent practical" and to prefer remedial actions in which treat- ment "permanently and significantly reduces the volume, toxic- ity, or mobility of hazardous substances, pollutants, and contami- nants as a principal element." The EPA Engineering Bulletins are a series of documents that summarize the available information on selected treatment and site remediation technologies and re- lated issues. They provide summaries and references of the lat- est information to help remedial project managers, on-scene coordinators, contractors, and other site cleanup managers un- derstand the type of data and site characteristics needed to evalu- ate a technology for potential applicability to their hazardous waste sites. Documents that describe individual site remediation tech- nologies focus on remedial investigation scoping needs. Addenda are issued periodically to update the original bulletins. Introduction This bulletin provides remedial project managers, on-scene coordinators, and other state or private remediation managers and their technical support personnel with information to facili- tate the selection of appropriate remedial alternatives for soil contaminated with arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg), and lead (Pb). This bulletin primarily condenses information that is included in a more comprehensive Technical Resource Document (TRD) entitled "Contaminants and Reme- dial Options at Selected Metal-Contaminated Sites [1]". Common compounds, transport, and fate are discussed for each of the five elements. A general description of metal-con- taminated Superfund soils is provided. The technologies cov- ered are immobilization [containment (caps, vertical barriers, hori- zontal barriers), solidification/stabilization (cement-based, poly- mer microencapsulation), and vitrification]; and separation and concentration (soil washing, pyrometallurgy, and soil flushing). Use of treatment trains is also addressed. Electrokinetics is addressed in the technical resource docu- ment, but not here, since it had not been demonstrated at full scale in the U.S. for metals remediation. Also, an update on the status of in situ electrokinetics for remediation of metal-contami- nated soil is in progress and should be available in the nearfu- Contents Section Purpose 1 Introduction 1 Overview of As, Cd, Cr, Hg, Pb, and Their Compounds 2 General Description of Superfund Soils Contaminated with As, Cd, Cr, Hg, and Pb 3 Soil Cleanup Goals for As, Cd, Cr, Hg, and Pb 3 Technologies for Containment and Remediation of As, Cd, Cr, Hg, and Pb in Soils 4 Specific Remedial Technologies 5 Use of Treatment Trains 15 Cost Ranges of Remedial Technologies 16 Sources of Additional Information 17 Acknowledgements 18 References.... ... 18 ------- ture [2]. Another change from the original technical resource docu- ment is that physical separation is addressed in the bulletin un- der soil washing, whereas it was previously covered as a sepa- rate topic. It is assumed that users of this bulletin will, as necessary, familiarize themselves with (1 ) the applicable or relevant and ap- propriate regulations pertinent to the site of interest; (2) appli- cable health and safety regulations and practices relevant to the metals and compounds discussed; and (3) relevant sampling, analysis, and data interpretation methods. The majority of the information on which this bulletin is based was collected during 1992 to 1994. Information on Pb battery (Pb, As), wood preserv- ing (As, Cr), pesticide (Pb, As, Hg), and mining sites is limited, as it was in the original technical resource document. Most of these site types have been addressed in other EPASuperfund documents [3][4][5][6][7][8]. The greatest emphasis is on reme- diation of inorganic forms of the metals of interest. Organometal- lic compounds, organic-metal mixtures, and multimetal mixtures are briefly addressed. At the time of this printing, treatment standards for Resource Conservation and Recovery Act (RCRA) wastes that contain met- als (in 40 CFR 268) and for contaminated media (in 40 CFR 269) are being investigated for potential revisions. These revi- sions may impact the selection of the technology for remediating sites containing these metal-bearing wastes. Overview of As, Cd, Cr, Hg, Pb Their Compounds This section provides a brief, qualitative overview of the physi- cal characteristics and mineral origins of the five metals, and factors affecting their mobility. More comprehensive and quanti- tative reviews of the behavior of these five metals in soil can be found in other readily available EPA Superfund documents Overview of Physical Characteristics Mineral Origins As is a semimetallic element or metalloid that has several allotropic forms. The most stable allotrope is a silver-gray, brittle, crystalline solid that tarnishes in air. As compounds, mainly As2O3, can be recovered as a by-product of processing complex ores mined mainly for copper, Pb, zinc, gold, and silver. As occurs in a wide variety of mineral forms, including arsenopyrite (FeAsS4), which is the main commercial ore of As worldwide. Cd is a bluish-white, soft, ductile metal. Pure Cd compounds rarely are found in nature, although occurrences of greenockite (CdS) and otavite (CdCO3) are known. The main sources of Cd are sulfide ores of Pb, zinc, and copper. Cd is recovered as a by- product when these ores are processed. Cr is a lustrous, silver-gray metal. It is one of the less com- mon elements in the earth's crust, and occurs only in compounds. The chief commercial source of Cr is the mineral chromite (FeCr2O4). Cr is mined as a primary product and is not recovered as a by-product of any other mining operation. There are no chromite ore reserves, nor is there primary production of chromite in the U.S.. Hg is a silvery, liquid metal. The primary source of Hg is cinnabar (HgS), a sulfide ore. In a few cases, Hg occurs as the principal ore product; it is more commonly obtained as the by- product of processing complex ores that contain mixed sulfides, oxides, and chloride minerals (these are usually associated with base and precious metals, particularly gold). Native or metallic Hg is found in very small quantities in some ore sites. The cur- rent demand for Hg is met by secondary production (i.e., recy- cling and recovery). Pb is a bluish-white, silvery, or gray metal that is highly lus- trous when freshly cut but tarnishes when exposed to air. It is very soft and malleable, has a high density (11.35 g/cm3) and low melting point (327. 4°C), and can be cast, rolled, and ex- truded. The most important Pb ore is galena (PbS). Recovery of Pb from the ore typically involves grinding, flotation, roasting, and smelting. Less common forms of the mineral are cerussite (PbCO3), anglesite (PbSO4), and crocoite (PbCrO4). Overview of Behavior of As, Cd, Cr, Pb, Since metals cannot be destroyed, remediation of metal- contaminated soil consists primarily of manipulating (i.e., exploit- ing, increasing, decreasing, or maintaining) the mobility of metal contaminant(s) to produce a treated soil that has an acceptable total or leachable metal content. Metal mobility depends upon numerous factors. As noted in reference [9]: "Metal mobility in soil-waste systems is determined by the type and quantity of soil surfaces present, the con- centration of metal of interest, the concentration and type of competing ions and complexing ligands, both organic and inorganic, pH, and redox status. Generalization can only serve as rough guides of the expected behavior of metals in such systems. Use of literature or laboratory data that do not mimic the specific site soil and waste system will not be adequate to describe or predict the behavior of the metal. Data must be site specific. Long term effects must also be considered. As organic con- stituents of the waste matrix degrade, or as pH or redox conditions change, either through natural processes of weathering or human manipulation, the potential mobil- ity of the metal will change as soil conditions change." Based on the above description of the number and type of factors affecting metal mobility, it is clear that a comprehensive and quantitative description of mobility of the five metals under all conditions is well beyond the scope of this bulletin. Thus, the behavior of the five metals are described below, but for a limited number of conditions. Cd, Cr(lll), and Pb are present in cationic forms under natural environmental conditions [9]. These cationic metals generally are not mobile in the environment and tend to remain relatively close to the point of initial deposition. The capacity of soil to adsorb cationic metals increases with increasing pH, cation exchange capacity, and organic carbon content. Under the neutral to basic conditions typical of most soils, cationic metals are strongly adsorbed on the clay fraction of soils and can be adsorbed by hydrous oxides of iron, aluminum, or manganese present in soil minerals. Cationic metals will precipitate as hydroxides, carbon- ates, or phosphates. In acidic, sandy soils, the cationic metals are more mobile. Under conditions that are atypical of natural soils (e.g., pH <5 or>9; elevated concentrations of oxidizers or reducers; high concentrations of soluble organic or inorganic complexing or colloidal substances), but may be encountered as a result of waste disposal or remedial processes, the mobility of these metals may be substantially increased. Also, competitive adsorption between various metals has been observed in ex- periments involving various solids with oxide surfaces (y FeOOH, cc-SIO2, and y-AI2O3). In several experiments, Cd adsorption was decreased by the addition of Pb or Cu for all three of these sol- Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- ids. The addition of zinc resulted in the greatest decrease of Cd adsorption. Competition for surface sites occurred when only a few percent of all surface sites were occupied [11]. As, Cr (VI), and Hg behaviors differ considerably from Cd, Cr (III), and Pb. As and Cr(VI) typically exist in anionic forms under environmental conditions. Hg, although it is a cationic metal, has unusual properties (e.g., liquid at room tempera- ture, easily transforms among several possible valence states). In most As-contaminated sites, As appears as As2O3 or as anionic As species leached from As2O3, oxidized to As (V), and then sorbed onto iron-bearing minerals in the soil. As may be present also in organometallic forms, such as methylarsenic acid (H2AsO3CH3) and dimethylarsenic acid ((CH3)2AsO2H), which are active ingredients in many pesticides, as well as the volatile compounds arsine (AsH3) and its methyl derivatives [i.e., dimethylarsine (HAs(CH3)2) and trimethylarsine (As(CH3)3)]. These As forms illustrate the various oxidation states that As commonly exhibits (-III, O.lll, and V) and the resulting complex- ity of its chemistry in the environment. As (V) is less mobile (and less toxic) than As (III). As (V) exhibits anionic behavior in the presence of water, and hence its aqueous solubility increases with increasing pH, and it does not complex or precipitate with other anions. As(V) can form low solubility metal arsenates. Calcium arsenate (Ca3(AsO4)2) is the most stable metal arsenate in well-oxidized and alkaline environments, but it is unstable in acidic environments. Even under initially oxidizing and alkaline conditions, absorption of CO2 from the air will result information of CaCO3and release of arsenate. In sodic soils, sufficient sodium is available, such that the mobile compound Na3AsO4 can form. The slightly less stable manganese arsenate (Mn2(AsO4)2) forms in both acidic and al- kaline environments, while iron arsenate is stable under acidic soil conditions. In aerobic environments, H3AsO4 predominates at pH <2 and is replaced by H2AsO4-, HAsO42" and AsO43' as pH increases to about 2, 7, and 11.5, respectively. Under mildly reducing conditions, H3AsO3 is a predominant species at low pH, but is replaced by H2AsO3", HAsO32~, and AsO33" as pH in- creases. Under still more reducing conditions and in the pres- ence of sulfide, As2S3 can form. As2S3 is a low-solubility, stable solid. AsS2 and AsS2- are thermodynamically unstable with re- spect to As2S3 [12]. Under extreme reducing conditions, elemen- tal As and volatile arsine (AsH3) can occur. Just as competition between cationic metals affects mobility in soil, competition between anionic species (chromate, arsenate, phosphate, sul- fate, etc.) affects anionic fixation processes and may increase mobility. The most common valence states of Cr in the earth's sur- face and near-surface environment are +3 (trivalent or Cr(lll)) and +6 (hexavalentorCr(VI)). The trivalent Cr (discussed above) is the most thermodynamically stable form under common en- vironmental conditions. Except in leathertanning, industrial ap- plications of Cr generally use the Cr(VI) form. Due to kinetic limitations, Cr (VI) does not always readily reduce to Cr (III) and can remain present over an extended period of time. Cr (VI) is present as the chromate (CrO42") or dichromate (Cr 2O 72~) anion, depending on pH and concentration. Cr (VI) anions are less likely to be adsorbed to solid surfaces than Cr (III). Most solids in soils carry negative charges that inhibit Cr (VI) adsorption. Although clays have high capacity to adsorb cationic metals, they interact little with Cr (VI) because of the similar charges carried by the anion and clay in the common pH range of soil and groundwater. The only common soil solid that adsorbs Cr(VI) is iron oxyhydroxide. Generally, a major portion of Cr(VI) and other anions adsorbed in soils can be at- tributed to the presence of iron oxyhydroxide. The quantity of Cr(VI) adsorbed onto the iron solids increases with decreasing pH. At metal-contaminated sites, Hg can be present in mercuric form (Hg2*) mercurous form (Hg22*), elemental form (Hg°), or alky- lated form (e.g., methyl and ethyl Hg). Hg22+ and Hg2+ are more stable under oxidizing conditions. Under mildly reducing condi- tions, both organically bound Hg and inorganic Hg compounds can convert to elemental Hg, which then can be readily con- verted to methyl or ethyl Hg by biotic and abiotic processes. Methyl and ethyl Hg are mobile and toxic forms. Hg is moderately mobile, regardless of the soil. Both the mercurous and mercuric cations are adsorbed by clay minerals, oxides, and organic matter. Adsorption of cationic forms of Hg increases with increasing pH. Mercurous and mercuric Hg also are immobilized by forming various precipitates. Mercurous Hg precipitates with chloride, phosphate, carbonate, and hydroxide. At concentrations of Hg commonly found in soil, only the phos- phate precipitate is stable. In alkaline soils, mercuric Hg precipi- tates with carbonate and hydroxide to form a stable (but not ex- ceptionally insoluble) solid phase. At lower pH and high chloride concentration, soluble HgCI2 is formed. Mercuric Hg also forms complexes with soluble organic matter, chlorides, and hydrox- ides that may contribute to its mobility [9]. In strong reducing conditions, HgS, a very low solubility compound is formed. Of with As, Cd, Cr, Hg, Pb Soils can become contaminated with metals from direct con- tact with industrial plant waste discharges; fugitive emissions; or leachate from waste piles, landfills, or sludge deposits. The spe- cific type of metal contaminant expected at a particular Super- fund site would obviously be directly related to the type of opera- tion that had occurred there. Table 1 lists the types of operations that are directly associated with each of the five metal contami- nants. Wastes at CERCLA sites are frequently heterogeneous on a macro and micro scale. The contaminant concentration and the physical and chemical forms of the contaminant and matrix usually are complex and variable. Of these, waste disposal sites collect the widest variety of waste types; therefore concentration profiles vary by orders of magnitude through a pit or pile. Limited volumes of high-concentration "hot spots" may develop due to variations in the historical waste disposal patterns or local trans- port mechanisms. Similar radical variations frequently occur on the particle-size scale as well. The waste often consists of a physi- cal mixture of very different solids, for example, paint chips in spent abrasive. Industrial processes may result in a variety of solid metal- bearing waste materials, including slags, fumes, mold sand, fly ash, abrasive wastes, spent catalysts, spent activated carbon, and refractory bricks [13]. These process solids may be found above ground as waste piles or below ground in landfills. Solid- phase wastes can be dispersed by well-intended but poorly con- trolled reuse projects. Waste piles can be exposed to natural disasters or accidents causing further dispersion. Cleanup for As, Cd, Cr, Hg, Pb Table 2 provides an overview of cleanup goals (actual and potential) for both total and leachable metals. Based on inspec- Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Table 1. Principal Sources of As, Cd, Cr, Hg, and Pb Contaminated Soils Contaminant Principal Sources As Cd Cr Hg Pb Wood preserving As-waste disposal Pesticide production and applica- tion Mining Plating Ni-Cd battery manufacturing Cd-waste disposal Plating Textile manufacturing Leather tanning Pigment manufacturing Wood preserving Cr-waste disposal Chloralkali manufacturing Weapons production Copper and zinc smelting Gas line manometer spills Paint application Hg-waste disposal Ferrous/nonferrous smelting Pb-acid battery breaking Ammunition production Leaded paint waste Pb-waste disposal Secondary metals production Waste oil recycling Firing ranges Ink manufacturing Mining Pb-acid battery manufacturing Leaded glass production Tetraethyl Pb production Chemical manufacturing tion of the total metals cleanup goals, one can see that they vary considerably both within the same metal and between metals. Similar variation is observed in the actual or potential leachate goals. The observed variation in cleanup goals has at least two implications with regard to technology alternative evaluation and selection. First, the importance of identifying the target metal(s), contaminant state (leachable vs. total metal), the specific type of test and conditions, and the numerical cleanup goals early in the remedy evaluation process is made apparent. Depending on which cleanup goal is selected, the required removal or leachate reduction efficiency of the overall remediation can vary by sev- eral orders of magnitude. Second, the degree of variation in goals both within and between the metals, plus the many factors that affect mobility of the metals (discussed earlier in the bulletin), suggest that generalizations about effectiveness of a technol- ogy for meeting total or leachable treatment goals should be viewed with some caution. Technologies for Containment of As, Cd, Cr, Hg, Pb in Soils Technologies potentially applicable to the remediation of soils contaminated with the five metals or their inorganic compounds are listed below. Underlined technologies have been implemented (not necessarily in all applicable modes—ex situ, in situ, off-site, and onsite) on numerous metal-contaminated soils and are avail- able from a substantial number of vendors. Bracketed technolo- gies have been operated or demonstrated on metal-contaminated soil with some success at full scale on one to approximately five soils, and some cost and performance data are available. In situ horizontal barriers are difficult to implement but are included to address in situ containment options for all contaminated soil de- posit surfaces. The remaining technology, electrokinetics, has been implemented at full-scale in Europe and not in the U.S. but is undergoing a Superfund Innovative Technology Evaluation (SITE) demonstration. As noted above, electrokinetics is not ad- dressed in the bulletin. Othertechnologies (e.g., phytoremediation and bacterial remediation) are being evaluated and may provide low-cost remediation for low concentration, large volume wastes, but these technologies are not addressed here due to their early stage of development and application to metal-contaminated soils. Technology Class Containment Solidification/ Stabilization Separation/ Concentration Specific Technology Caps, Vertical Barriers. Horizontal Barriers Cement-Based [Polymer MicroencapsulationJ [Vitrification] [Soil Washing] [Soil Flushing (In Situ Only)] [Pyrometallurgy] Electrokinetics (Addressed in TRD only) For each technology listed above, the following topics are discussed: • Process description • Site requirements for technology implementation « Applicability • Performance in treating metals in soil and Best Demon- strated Available Technology (BOAT) status • Technologies in the SITE Demonstration Program • EPA contact for the technology The BOAT status of the technology (see fourth bullet above) refers to the determination underthe RCRAofthe BDATforvari- ous industry-generated hazardous wastes that contain the met- als of interest. Whether the characteristics of a Superfund metal- contaminated soil (or fractions derived from it) are similar enough to the RCRA waste to justify serious evaluation of the BOAT for a specific Superfund soil must be made on a site specific basis. Other limitations relevant to BDATs include (1) the regulatory basis for BOAT standards focus BDATs on proven, commercially available technologies at the time of the BOAT determination, (2) a BOAT may be identified, but that does not necessarily pre- clude the use of Othertechnologies, and (3) a technology identi- fied as BOAT may not necessarily be the current technology of choice in the RCRA hazardous waste treatment industry. The EPA's SITE program (referred to in the fifth bullet above) evaluates many emerging and demonstrated technologies in or- der to promote the development and use of innovative technolo- gies to clean up Superfund sites across the country. The major focus of SITE is the Demonstration Program, which is designed to provide engineering and cost data for selected technologies. Cost is not discussed in each technology narrative; how- ever, a summary table is provided at the end of the technology Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Table 2. Cleanup Goals (Actual and Potential) for Total and teachable Metals Description As Cd Cr (Total) Hg Pb Total Metals Goals (mg/Kg) Background (Mean) [1] 5 Background (Range) [1] 1 to 50 Superfund Site Goals from TRD [1 ] 5 to 65 Theoretical Minimum Total Metals to 100 Ensure TCLP Leachate < Threshold (i.e., TCLP X 20) California Total Threshold 500 Limit Concentration [1] teachable Metals (u.g/L) TCLP Threshold for RCRA Waste 5000 (SW846, Method 1311) Extraction Procedure Toxicity Test 5000 (EP Tox) (Method 1310) Synthetic Precipitate Leachate — Procedure (Method 1312) Multiple Extraction Procedure — (Method 1320) California Soluble Threshold 5000 Leachate Concentration 0.06 0.01 to 0.70 3 to 20 20 100 1000 1000 100 1 to 1000 6.7 to 375 100 500 5000 5000 0.03 0.01 to 0.30 1 to 21 4 20 200 200 10 2 to 200 200 to 500 100 1000 5000 5000 1000 5000 200 5000 Maximum Contaminant Level3 Superfund Site Goals from TRD [1] 50 50 5 100 50 2 0.05 to 2 15 50 Maximum Contaminant Level = The maximum permissible level of contaminant in water delivered to any user of a public system. • No specified level and no example cases identified. discussion section that illustrates technology cost ranges and treatment train options. Technologies Containment Containment technologies for application at Superfund sites include landfill covers (caps), vertical barriers, and horizontal bar- riers [1], For metal remediation, containment is considered an established technology except for in situ installation of horizontal barriers. This bulletin does not address construction of onsite landfill liners for placement of excavated material from the site. Process Description—Containment ranges from a surface cap that limits infiltration of uncontaminated surface waterto sub- surface vertical or horizontal barriers that restrict lateral or verti- cal migration of contaminated groundwater. In addition to the con- tainment documents referenced in this section, six other EPA containment documents are noted in the final section of this en- gineering bulletin on covers, liners, Quality Assurance/Quality Control (QA/QC) for geomembrane seams, and QA/QC for con- tainment construction. Containment is covered primarily by ref- erence in the original technical resource document. The text pro- vided here is primarily from reference [5] on remediation of wood preserving sites. Caps—Capping systems reduce surface water infiltration; control gas and odor emissions; improve aesthetics; and provide a stable surface over the waste. Caps can range from a simple native soil cover to a full RCRA Subtitle C, composite cover. Cap construction costs depend on the number of compo- nents in the final cap system (i.e., costs increase with the addi- tion of barrier and drainage components). Additionally, cost es- calates as a function of topographic relief. Side slopes steeper than 3 horizontal to 1 vertical can cause stability and equipment problems that dramatically increase the unit cost. Vertical Barriers—Vertical barriers minimize the movement of contaminated groundwater off-site or limit the flow of uncon- taminated groundwater onsite. Common vertical barriers include slurry walls in excavated trenches; grout curtains formed by in- jecting grout into soil borings; vertically-injected, cement-bento- nite grout-filled borings or holes formed by withdrawing beams driven into the ground; and sheet-pile walls formed of driven steel. Certain compounds can affect cement-bentonite barriers. The impermeability of bentonite may significantly decrease when it is exposed to high concentrations of creosote, water-soluble salts (copper, Cr, As), or fire retardant salts (borates, phosphates, and ammonia). Specific gravity of salt solutions must be greater than 1.2 to impact bentonite [14][15]. In general, soil-bentonite blends resist chemical attack best if they contain only 1 percent bentonite and 30 to 40 percent natural soil fines. Treatability tests should evaluate the chemical stability of the barrier if adverse conditions are suspected. Carbon steel used in pile walls quickly corrodes in dilute acids, slowly corrodes in brines or salt water, and remains mostly unaffected by organic chemicals or water. Salts and fire retar- dants can reduce the service life of a steel sheet pile; corrosion- resistant coatings can extend their anticipated life. Major steel suppliers will provide site-specific recommendations for cathodic protection of piling. Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Construction costs for vertical barriers are influenced by the soil profile of the barrier material used and by the method of placing it. The most economical shallow vertical barriers aresoil- bentonite trenches excavated with conventional backhoes; the most economical deep vertical barriers consist of a cement-ben- tonite wall placed by a vibrating beam. Horizontal Barriers—In situ horizontal barriers can under- lie a sector of contaminated materials onsite without removing the hazardous waste or soil. Established technologies use grout- ing techniques to reduce the permeability of underlying soil lay- ers. Studies performed by the U.S. Army Corps of Engineers (COE) [16] indicate that conventional grout technology cannot produce an impermeable horizontal barrier because it cannot ensure uniform lateral growth of the grout. These same studies found greater success with jet grouting techniques in soils that contain fines sufficient to prevent collapse of the wash hole and that present no large stones or boulders that could deflect the cutting jet. Since few in situ horizontal barriers have been constructed, accurate costs have not been established. Work performed by COE for EPA has shown that it is very difficult to form effective horizontal barriers. The most efficient barrier installation used a jet wash to create a cavity in sandy soils into which cement- bentonite grouting was injected. The costs relate to the number of borings required. Each boring takes at least one day to drill. Site Requirements—In general, the site must be suitable for a variety of heavy construction equipment including bulldoz- ers, graders, backhoes, multi-shaft drill rigs, various rollers, vi- bratory compactors, forklifts, and seaming devices [18]. When capping systems are being utilized, onsite storage areas are nec- essary for the materials to be used in the cover. If site soils are adequate for use in the cover, a borrow area needs to be identi- fied and the soil tested and characterized. If site soils are not suitable, it may be necessary to truck in other low-permeability soils [18]. In addition, an adequate supply of water may also be needed in order to achieve the optimum soil density. The construction of vertical containment barriers, such as slurry walls, requires knowledge of the site, the local soil and hydrogeologic conditions, and the presence of underground utili- ties [17]. Preparation of the slurry requires batch mixers, hydra- tion ponds, pumps, hoses, and an adequate supply of water. Therefore, onsite water storage tanks and electricity are neces- sary. In addition, areas adjacent to the trench need to be avail- able for the storage of trench spoils (which could potentially be contaminated) and the mixing of backfill. If excavated soils are not acceptable for use as backfill, suitable backfill must be trucked onto the site [17]. Applicability—Containment is most likely to be applicable to (1) wastes that are low-hazard (e.g., low toxicity or low con- centration) or immobile; (2) wastes that have been treated to produce low hazard or low mobility wastes for onsite disposal; or (3) wastes whose mobility must be reduced as a temporary mea- sure to mitigate risk until a permanent remedy can be tested and implemented. Situations where containment would not be appli- cable include (1) wastes for which there is a more permanent and protective remedy that is cost-effective, (2) where effective placement of horizontal barriers below existing contamination is difficult; and (3) where drinking water sources will be adversely affected if containment fails, and if there is inadequate confidence in the ability to predict, detect, or control harmful releases due to containment failure. Important advantages of containment are (1) surface caps and vertical barriers are relatively simple and rapid to implement at low cost and can be more economical than excavation and removal of waste; (2) caps and vertical barriers can be applied to large areas or volumes of waste; (3) engineering control (con- tainment) is achieved, and may be a final action if metals are well immobilized and potential receptors are distant; (4) a variety of barrier materials are available commercially; and (5) in some cases it may be possible to create a land surface that can sup- port vegetation and/or be applicable for other purposes. Disad- vantages of containment include (1) design life is uncertain; (2) contamination remains onsite, available to migrate should con- tainment fail; (3) long-term inspection, maintenance and moni- toring is required; (4) site must be amenable to effective monitor- ing; and (5) placement of horizontal barriers below existing waste is difficult to implement successfully. Performance and BOAT Status—Containment is widely ac- cepted as a means of controlling the spread of contamination and preventing the future migration of waste constituents. Table 3 shows a list of selected sites where containment has been selected for remediating metal-contaminated solids. The performance of capping systems, once installed, may be difficult to evaluate [18], Monitoring well systems or infiltration monitoring systems can provide some information, but it is often not possible to determine whether the water or leachate origi- nated as surface water or groundwater. With regard to slurry walls and other vertical containment barriers, performance may be affected by a number of variables including geographic region, topography, and material availabil- ity. A thorough characterization of the site and a compatibility study are highly recommended [17]. Containment technologies are not considered "treatment technologies" and hence no BDATs involving containment have been established. Table 3. Containment Selections/Applications at Selected Superfund Sites With Metal Contamination Site Name/State Ninth Avenue Dump, IN Industrial Waste Control, AK E.H. Shilling Landfill, OH Chemtronic, NC Ordnance Works Disposal, WV Industriplex, MA Specific Technology Containment-Slurry Wall Containment-Slurry Wall Containment-Slurry Wall Capping Capping Capping Key Metal Contaminants Pb As, Cd, Cr, Pb As Cr, Pb As, Pb As, Pb, Cr Associated Technology Slurry Wall/Capping Capping/French Drain Capping/Clay Berm Capping Capping Capping Status3 S I S S S I 1 Status codes as of February 1996: S = selected in ROD; I = in operation. Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- SITE Program Demonstration Projects—Ongoing SITE demonstrations applicable to soils contaminated with the metals of interest include « Morrison Knudsen Corporation (High clay grouting tech- nology) • RKK, Ltd. (Frozen soil barriers) Contact—Technology-specific questions regarding contain- ment may be directed to Mr. David Carson (NRMRL) at (513) 569-7527. Technologies Solidification/stabilization (SIS), as used in this engineering bulletin, refers to treatment processes that mix or inject treat- ment agents into the contaminated material to accomplish one or more of the following objectives: • Improve the physical characteristics of the waste by pro- ducing a solid from liquid or semiliquid wastes. • Reduce the contaminant solubility by formation of sorbed species or insoluble precipitates (e.g., hydroxides, car- bonates, silicates, phosphates, sulfates, orsulfides). • Decrease the exposed surface area across which mass transfer loss of contaminants may occur by formation of a crystalline, glassy, or polymeric framework which sur- rounds the waste particles. • Limit the contact between transport fluids and contami- nants by reducing the material's permeability [1]. SIS technology usually is applied by mixing contaminated soils or treatment residuals with a physical binding agent to form a crystalline, glassy, or polymeric framework surrounding the waste particles. In addition to the microencapsulation, some chemical fixation mechanisms may improve the waste's leach resistance. Other forms of S/S treatment rely on macroencapsulation, where the waste is unaltered but macro- scopic particles are encased in a relatively impermeable coating [19], or on specific chemical fixation, where the contaminant is converted to a solid compound resistant to leaching. S/S treat- ment can be accomplished primarily through the use of either inorganic binders (e.g., cement, fly ash, and/or blast furnace slag) or by organic binders such as bitumen [1 ]. Additives may be used, for example, to convert the metal to a less mobile form or to counteract adverse effects of the contaminated soil on the S/S mixture (e.g., accelerated or retarded setting times, and low physi- cal strength). The form of the final product from S/S treatment can range from a crumbly, soil-like mixture to a monolithic block. S/S is more commonly done as an ex situ process, but the in situ option is available. The full range of inorganic binders, organic binders, and additives is too broad to be covered here. The em- phasis in this bulletin is on ex situ, cement-based S/S, which is widely used; in situ, cement-based S/S, which has been applied to metals at full-scale; and polymer microencapsulation, which appears applicable to certain wastes that are difficult to treat via cement-based S/S. Additional information and references on solidification/sta- bilization of metals can be found in the source technical resource document for this bulletin [1] and Engineering Bulletin: Solidifi- cation and Stabilization ofOrganics and Inorganics, EPA/540/S- 92/015 [20], Also, Chemical Fixation and Solidification of Haz- ardous Wastes [21] is probably the most comprehensive refer- ence on S/S of metals (692 pages total, 113 pages specifically on fixation of metals). It is available in several EPA libraries. In- novative S/S technologies (e.g., sorption and surfactant pro- cesses, bituminization, emulsified asphalt, modified sulfur ce- ment, polyethylene extrusion, soluble silicate, slag, lime, and soluble phosphates) are addressed in Innovative Site Remedia- tion Technology—Solidification/Stabilization, Volume 4 [22]. Process Description—Ex situ, cement-based S/S is per- formed on contaminated soil that has been excavated and clas- sified to reject oversize. Cement-based S/S involves mixing con- taminated materials with an appropriate ratio of cement or simi- lar binder/stabilizer, and possibly water and other additives. A system is also necessary for delivering the treated wastes to molds, surface trenches, or subsurface injection. Off-gas treat- ment (if volatiles or dust are present) may be necessary. The fundamental materials used to perform this technology are Port- land-type cements and pozzolanic materials. Portland cements are typically composed of calcium silicates, aluminates, aluminoferrites, and sulfates. Pozzolans are very small spheroi- dal particles that are formed in combustion of coal (fly ash) and in lime and cement kilns, for example. Pozzolans of high silica content are found to have cement-like properties when mixed with water. Cement-based S/S treatment may involve using only Portland cement, only pozzolanic materials, or blends of both. The composition of the cement and pozzolan, together with the amount of water, aggregate, and other additives, determines the set time, cure time, pour characteristics, and material properties (e.g., pore size, compressive strength) of the resulting treated waste. The composition of cements and pozzolans, including those commonly used in S/S applications, are classified accord- ing to American Society for Testing and Materials (ASTM) stan- dards. S/S treatment usually results in an increase (>50% in some cases) in the treated waste volume. Ex situ treatment provides high throughput (100 to 200 yd3/day/mixer). Cement-based S/S reduces the mobility of inorganic com- pounds by formation of insoluble hydroxides, carbonates, or sili- cates; substitution of the metal into a mineral structure; sorption; physical encapsulation; and perhaps other mechanisms. Cement- based S/S involves a complex series of reactions, and there are many potential interferences (e.g., coating of particles by organ- ics, excessive acceleration or retardation of set times by various soluble metal and inorganic compounds; excessive heat of hy- dration; pH conditions that solubilize anionic species of metal compounds, etc.) that can prevent attainment of S/S treatment objectives for physical strength and teachability. While there are many potential interferences, Portland cement is widely used and studied, and a knowledgeable vendor may be able to identify, and confirm via treatability studies, approaches to counteract adverse effects by use of appropriate additives or other changes in formulation. In situ, cement-based solidification/stabilization has only two steps: (1) mixing and (2) off-gas treatment. The processing rate for in situ S/S is typically considerably lower than for ex situ processing. In situ S/S is demonstrated to depths of 30 feet and may be able to extend to 150 feet. The most significant chal- lenge in applying S/S in situ for contaminated soils is achieving complete and uniform mixing of the binder with the contaminated matrix [23]. Three basic approaches are used for in situ mixing of the binder with the matrix: (1) vertical auger mixing; (2) in- place mixing of binder reagents with waste by conventional earthmoving equipment, such as draglines, backhoes, or clamshell buckets; and (3) injection grouting, which involves forc- ing a binder containing dissolved or suspended treatment agents into the subsurface, allowing it to permeate the soil. Grout injec- tion can be applied to contaminated formations lying well below the ground surface. The injected grout cures in place to produce an in situ treated mass. Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- S/S by polymer microencapsulation can include applica- tion of thermoplastic orthermosetting resins. Thermoplastic ma- terials are the most commonly used organic-based S/S treat- ment materials. Potential candidate resins for thermoplastic en- capsulation include bitumen, polyethylene and other polyolefins, paraffins, waxes, and sulfur cement. Of these candidate thermo- plastic resins, bitumen (asphalt) is the least expensive and by far the most commonly used [24]. The process of thermoplastic en- capsulation involves heating and mixing the waste material and the resin at elevated temperature, typically 130°C to 230°C in an extrusion machine. Any water or volatile organics in the waste boil off during extrusion and are collected for treatment or dis- posal. Because the final product is a stiff, yet plastic resin, the treated material typically is discharged from the extruder into a drum or other container. S/S process quality control requires information on the range of contaminant concentrations; potential interferences in waste batches awaiting treatment; and treated product properties such as compressive strength, permeability, teachability, and in some instances, toxicity [20]. Site Requirements—The site must be prepared forthe con- struction, operation, maintenance, decontamination, and decom- missioning of the equipment. The size of the area required for the process equipment depends on several factors, including the type of S/S process involved, the required treatment capacity of the system, and site characteristics, especially soil topography and load-bearing capacity. A small mobile ex situ unit occupies space for two, standard flatbed trailers. An in situ system requires a larger area to accommodate a drilling rig as well as a larger area for auger decontamination. Applicability—This section addresses expected applicability based on the chemistry of the metal and the S/S binders. The soil-contaminant-binder equilibrium and kinetics are complicated, and many factors influence metal mobility, so there may be ex- ceptions to the generalizations presented below. For cement-based S/S, if a single metal is the predominant contaminant in soil, then Cd and Pb are the most amenable to cement-based S/S. The predominant mechanism for immobili- zation of metals in Portland and similar cements is precipitation of hydroxides, carbonates, and silicates. Both Pb and Cd tend to form insoluble precipitates in the pH ranges found in cured ce- ment. They may resolubilize, however, if the pH is not carefully controlled. For example, Pb in aqueous solutions tends to resolubilize as Pb(OH)3" around pH 10 and above. Hg, while it is a cationic metal like Pb and cadmium, does not form low solubil- ity precipitates in cement, so it is difficult to stabilize reliably by cement-based processes, and this difficulty would be expected to be greater with increasing Hg concentration and with organomercury compounds. As, due to its formation of anionic species, also does not form insoluble precipitates in the high pH cement environment, and cement-based solidification is gener- ally not expected to be successful. Cr(VI) is difficult to stabilize in cement due to formation of anions that are soluble at high pH. However, Cr (VI) can be reduced to Cr (III), which does form insoluble hydroxides. Although Hg and As (III and V) are particu- larly difficult candidates for cement-based S/S, this should not necessarily eliminate S/S (even cement-based) from consider- ation since (1) as with Cr (VI) it may be possible to devise a multistep process that will produce an acceptable product for cement-based S/S; (2) a non-cement based S/S process (e.g., lime and sulfide for Hg; oxidation to As (V) and coprecipitation with iron) may be applicable; or (3) the leachable concentration of the contaminant may be sufficiently low that a highly efficient S/S process may not be required to meet treatment goals. The discussion of applicability above also applies to in situ, cement-based S/S. If in situ treatment introduces chemical agents into the ground, this chemical addition may cause a pol- lution problem in itself, and may be subject to additional require- ments under the Land Disposal Restrictions. Polymer microencapsulation has been mainly used to treat low-level radioactive wastes. However, organic binders have been tested or applied to wastes containing chemical contaminants such as As, metals, inorganic salts, polychlorinated biphenyls (PCBs), and dioxins [24]. Polymer microencapsulation is particu- larly well suited to treating water-soluble salts such as chlorides or sulfates that generally are difficult to immobilize in a cement- based system [25]. Characteristics of the organic binder and extrusion system impose compatibility requirements on the waste material. The elevated operating temperatures place a limit on the quantity of water and volatile organic chemicals (VOCs) in the waste feed. Low volatility organics will be retained in the bitu- men but may act as solvents causing the treated product to be too fluid. The bitumen is a potential fuel source so the waste should not contain oxidizers such as nitrates, chlorates, or per- chlorates. Oxidants present the potential for rapid oxidation, caus- ing immediate safety concerns, as well as slow oxidation that results in waste form degradation. Wastes containing more than one metal are not addressed here, other than to say that cement-based solidification/stabili- zation of multiple metal wastes will be particularly difficult if a set of treatment and disposal conditions cannot be found that simul- taneously produces low mobility species for all the metals of con- cern. For example, the relatively high pH conditions that favor Pb immobilization would tend to increase the mobility of As. On the other hand, the various metal species in a multiple metal waste may interact (e.g., formation of low solubility compounds by com- bination of Pband arsenate)to produce a low mobility compound. Organic contaminants are often present with inorganic con- taminants at metal-contaminated sites. S/S treatment of organic- contaminated waste with cement-based binders is more com- plex than treatment of inorganics alone. This is particularly true with VOCs where the mixing process and heat generated by cement hydration reactions can increase vapor losses [26][27][28][29]. However, S/S can be applied to wastes that con- tain lower levels of organics, particularly when inorganics are present and/orthe organics are semivolatile or nonvolatile. Also, recent studies indicate the addition of silicates or modified clays to the binder system may improve S/S performance with organ- ics [19]. Performance and BOAT status—S/S with cement-based and pozzolan binders is a commercially available, established technology. Table 4 shows a selected list of sites where S/S has been selected for remediating metal-contaminated solids. At 12 of the 19 sites, S/S has been either completely or partially imple- mented. Note that S/S has been used to treat all five metals (Cr, Pb, As, Hg, and Cd). Although it would not generally be expected (forthe reasons noted in the previous section) that cement-based S/S would be applied to As and Hg contaminated soils, it was beyond the scope of this project to examine in detail the charac- terization data, S/S formulations, and performance data upon which the selections were based, so the selection/implementa- tion data are presented without further comment. Applications of polymer microencapsulation have been lim- ited to special cases where the specific performance features are required forthe waste matrix, and contaminants allow reuse of the treated waste as a construction material [30]. S/S is a BOAT forthe following waste types: Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Table 4. Solidification/Stabilization Selections/Applications at Selected Superfund Sites With Metal Contamination Site Name/State Specific Technology Key Metal Contaminants Associated Technology Status3 DeRewal Chemical, NJ Marathon Battery Co., NY Nascolite, Millville, NJ Roebling Steel, NJ Waldick Aerospace, NJ Aladdin Plating, PA Palmerton Zinc, PA Tonolli Corp., PA Solidification Chemical fixation Stabilization of wetland soils Solidification/stabilization (34-acre slag area) S/S,4,OOOcy Stabilization, 1 2,000 cy Stabilization, fly ash, lime, potash S/S Cr, Cd, Pb Cd, Ni Pb As, Cr, Pb Cd, Cr Cr Cd, Pb As, Pb GW pump and treatment Dredging, off-site disposal On-site disposal of stabilized soils; excavation and off-site disposal of wetland soils Capping LTTD, off-site disposal Off-site disposal — In situ chemical limestone S I S S C C I S Whitmoyer Laboratories, PA Bypass 601, NC Oxidation/fixation S/S As Cr, Pb barrier GW pump and treatment, capping, grading, and revegetation Capping, regrading, revegetation, GWpump and treatment Flowood, MS Independent Nail, SC Pepper's Steel and Alloys, FL Gurley Pit, AR Pesses Chemical, TX E.I. Dupontde Nemours, IA Shaw Avenue Dump, IA Frontier Hard Chrome, WA Gould Site, OR S/S, 6,000 cy S/S S/S In situ S/S Stabilization S/S S/S Stabilization S/S Pb Cd, Cr As, Pb Pb Cd Cd, Cr, Pb As, Cd Cr Pb Capping Capping On-site disposal Concrete capping Capping, regrading, and revegetation Capping, groundwater monitoring Capping, regrading, and revegetation C C C C C C C S I 1 Status codes as of February 1996: S = selected in ROD; I = in operation, not complete; C = completed. • Cd nonwastewaters (other than Cd-containing batteries) • Cr nonwastewaters such as D007 and U032 [following reduction to Cr(lll)] • Pb nonwastewaters such as D008, P110, U144, U145, and U146 • Wastes containing low concentrations (< 260 mg/Kg) of elemental Hg—sulfide precipitation • Plating wastes and steelmaking wastes Although vitrification, not S/S, was selected as BOAT for RCRA As-containing nonwastewaters, EPA does not preclude the use of S/S for treatment of As (particularly inorganic As) wastes but recommends that its use be determined on a case- by-case basis. A variety of stabilization techniques including ce- ment, silicate, pozzolan, and ferric coprecipitation were evalu- ated as candidate BDATs for As. Due to concerns about long- term stability and the waste volume increase, particularly with ferric coprecipitation, stabilization was not accepted as BOAT. SITE Program Demonstration Projects—Completed or on- going SITE demonstrations applicable to soils contaminated with the metals of interest include Completed • Advanced Remediation Mixing, Inc. (Ex situ S/S) • Funderburk & Associates (Ex situ S/S) • Geo-Con, Inc. (In situ S/S) • Soliditech, Inc. (Ex situ S/S) • STC Omega, Inc. ( Ex situ S/S) • WASTECH Inc. (Ex situ S/S) Ongoing Separation and Recovery Systems, Inc. (Ex situ S/S) WheelabratorTechnologies Inc. (Ex situ S/S) Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Contact—Technology-specific questions regarding S/S may be directed to Mr. Ed Earth (NRMRL) at (513) 569-7669. ¥itrification Vitrification applies high temperature treatment aimed pri- marily at reducing the mobility of metals by incorporation into a chemically durable, leach resistant, vitreous mass. Vitrification can be carried out on excavated soils as well as in situ. Process Description—During the vitrification process, or- ganic wastes are pyrolyzed (in situ) or oxidized (ex situ) by the melt front, whereas inorganics, including metals, are incorpo- rated into the vitreous mass. Off-gases released during the melt- ing process, containing volatile components and products of com- bustion and pyrolysis, must be collected and treated [1][31]. Vit- rification converts contaminated soils to a stable glass and crys- talline monolith [32]. With the addition of low-cost materials such as sand, clay, and/or native soil, the process can be adjusted to produce products with specific characteristics, such as chemical durability. Waste vitrification may be able to transform the waste into useful, recyclable products such as clean fill, aggregate, or higher valued materials such as erosion-control blocks, paving blocks, and road dividers. Ex situ vitrification technologies apply heat to a melter through a variety of sources such as combustion of fossil fuels (coal, natural gas, and oil) or input of electric energy by direct joule heat, arcs, plasma torches, and microwaves. Combustion or oxidation of the organic portion of the waste can contribute significant energy to the melting process, thus reducing energy costs. The particle size of the waste may need to be controlled for some of the melting technologies. For wastes containing re- fractory compounds that melt above the unit's nominal process- ing temperature, such as quartz or alumina, size reduction may be required to achieve acceptable throughputs and a homoge- neous melt. For high-temperature processes using arcing or plasma technologies, size reduction is not a major factor. For the intense melters using concurrent gas-phase melting or mechani- cal agitation, size reduction is needed for feeding the system and for achieving a homogeneous melt. In situ vitrification (ISV) technology is based on electric melter technology, and the principle of operation is joule heating, which occurs when an electrical current is passed through a region that behaves as a resistive heating element. Electrical current is passed through the soil by means of an array of electrodes in- serted vertically into the surface of the contaminated soil zone. Because dry soil is not conductive, a starter path of flaked graphite and glass frit is placed in a small trench between the electrodes to act as the initial flow path for electricity. Resistance heating in the starter path transfers heat to the soil, which then begins to melt. Once molten, the soil becomes conductive. The melt grows outward and downward as power is gradually increased to the full constant operating power level. A single melt can treat a re- gion of up to 1000 tons. The maximum treatment depth has been demonstrated to be about 20 feet. Large contaminated areas are treated in multiple settings that fuse the blocks together to form one large monolith [1], Further information on in situ vitrifi- cation can be found in the Engineering Bulletin: In Situ Vitrifica- tion Treatment, EPA/540/S-94/504 [33]. Site Requirements—The site must be prepared forthe mo- bilization, operation, maintenance, and demobilization of the equipment. Site activities such as clearing vegetation, removing overburden, and acquiring backfill material are often necessary for ex situ as well as in situ vitrification. Ex situ processes will require areas for storage of excavated, treated, and possibly pre- treated materials. The components of one ISV system are con- tained in three transportable trailers: an off-gas and process con- trol trailer, a support trailer, and an electrical trailer. The trailers are mounted on wheels sufficient for transportation to and over a compacted ground surface [34]. The field-scale ISV system evaluated in the SITE program required three-phase electrical power at either 12,500 or 13,800 volts, which is usually taken from a utility distribution system [35], Alternatively, the power may be generated onsite by means of a diesel generator. Typical applications require 800 kilowatt hours/ton (kWh/ton)to 1,000 kWh/ton [33]. Applicability—Setting cost and implementability aside, vit- rification should be most applicable where nonvolatile metal con- taminants have glass solubilities exceeding the level of contami- nation in the soil. Cr-contaminated soil should pose the least difficulties for vitrification, since it has low volatility, and a glass solubility between 1% and 3%. Vitrification may or may not be applicable for Pb, As, and Cd, depending on the level of difficulty encountered in retaining the metals in the melt, and controlling and treating any volatile emissions that may occur. Hg clearly poses problems for vitrification due to high volatility and low glass solubility (<0.1%) but may be allowable at very low concentra- tions (see Performance and BOAT section that follows). Chlorides present in the waste in excess of about 0.5 weight percent typically will not be incorporated into and discharged with the glass but will fume off and enter the off-gas treatment system. If chlorides are excessively concentrated, salts of alkali, alkaline earths, and heavy metals will accumulate in solid resi- dues collected by off-gas treatment. Separation of the chloride salts from the other residuals may be required before or during return of residuals to the melter. When excess chlorides are present, there is also a possibility that dioxins and furans may form and enter the off-gas treatment system. Waste matrix composition affects the durability of the treated waste. Sufficient glass-forming materials (SiO2) (>30 wt %) and combined alkali (Na + K)(>1.4wt%)are required for vitrification of wastes. If these conditions are not met, frit and/or flux addi- tives typically are needed. Vitrification is also potentially appli- cable to soils contaminated with mixed metals and metal-organic wastes. Specific situations where ex situ vitrification would not be applicable orwould face additional implementation problems in- clude (1) wastes containing > 25% moisture content cause ex- cessive fuel consumption; (2) wastes where size reduction and classification are difficult or expensive; (3) volatile metals, par- ticularly Cd and Hg, will vaporize and must be captured and treated separately; (4) As-containing wastes may require pre- treatment to produce less volatile forms; (5) metal concentra- tions in soil that exceed their solubility in glass; and (6) sites where commercial capacity is not adequate or transportation cost to a fixed facility is unacceptable. Specific situations, in addition to those cited above, where in situ vitrification would not be applicable orwould face addi- tional implementation problems include (1) metal-contaminated soil where a less costly and adequately protective remedy ex- ists; (2) projects that cannot be undertaken because of limited commercial availability; (3) contaminated soil <6 feet and >20 feet below the ground surface; (4) presence of an aquifer with high hydraulic conductivity (e.g., soil permeability >1 X 10"5 cm/ sec) limits economic feasibility due to excessive energy required; (5) contaminated soil mixed with buried metal that can result in a conductive path causing short circuiting of electrodes; (6) con- taminated soil mixed with loosely packed rubbish or buried coal 10 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- can start underground fires and overwhelm off-gas collection and treatment system; (7) volatile heavy metals nearthe surface can be entrained in combustion product gases and not retained in melt; (8) sites where surface slope >5% may cause melt to flow; (9) in situ voids >150 m3 interrupt conduction and heat transfer; and (10) underground structures and utilities <20 feet from the melt zone must be protected from heat or avoided. Where it can be successfully applied, advantages of vitrifi- cation include (1) vitrified product is an inert, impermeable solid that should reduce leaching for long periods of time; (2) volume of vitrified product will typically be smaller than initial waste vol- ume; (3) vitrified product may be usable; (4) a wide range of inorganic and organic wastes can be treated; and (5) there is both an ex situ and an in situ option available. A particular ad- vantage of ex situ treatment is better control of processing pa- rameters. Also, fuel costs may be reduced for ex situ vitrification by the use of combustible waste materials. This fuel cost-saving option is not directly applicable for in situ vitrification, since com- bustibles would increase the design and operating requirements for gas capture and treatment. Performance and BOAT Status—In situ vitrification has been implemented to date at one metal-contaminated Super- fund site (Parsons/ETM, Grand Ledge, Ml) and was evaluated underthe SITE Program [36]. The demonstration was completed in April 1994. About 3,000 cubic yards of soil were remediated. Some improvements are needed with melt containment and air emission control systems. The Innovative Technology Evalua- tion Report is now available from EPA [37]. ISV has been oper- ated at a large scale ten times, including two demonstrations on radioactively contaminated sites at the DOE's Hanford Nuclear Reservation [31][38], Pilot-scale tests have been conducted at Oak Ridge National Laboratory, Idaho National Engineering Labo- ratory, and Arnold Engineering Development Center. More than 150 tests and demonstrations at various scales have been per- formed on a broad range of waste types in soils and sludges. The technology has been selected as a preferred remedy at 10 private, Superfund, and DOD sites [39]. Table 5 provides a sum- mary of ISV technology selection/application at metal-contami- nated Superfund sites. A number of ex situ vitrification systems are under development. The technical resource document iden- Table 5. In Situ Vitrification Selections/Applications at Selected Su- perfund Sites With Metal Contamination Site Name/State Key Metal Contaminants Status3 Parsons Chemical, Ml Rocky Mountain Arsenal, CO Hg (low) As, Hg S/D Status codes as of February 1996: C = completed; S/D = selected, but subsequently de-selected. tified one full-scale ex situ melter that was reported to be operat- ing on RCRAorganics and inorganics. Vitrification is a BOAT for the following waste types: As-con- taining wastes including K031, K084, K101, K102, D004, and As-containing P and U wastes. SITE Program Demonstration Projects—Completed or on- going SITE demonstrations applicable to soils contaminated with the metals of interest include Completed • Babcock & Wilcox Co. (Cyclone furnace—ex situ vitrifica- tion) • Retech, Inc. (Plasma arc—ex situ vitrification) • Geosafe Corporation (In situ vitrification) Ongoing * Vortec Corporation (Ex situ oxidation and vitrification pro- cess) Three additional projects were completed in the SITE Emerging Technology program. Contact—Technology-specific questions regarding vitrifica- tion may be directed to Ms. Teri Richardson (NRMRL) at (513) 569-7949. Soil washing is an ex situ remediation technology that uses a combination of physical separation and aqueous-based sepa- ration unit operations to reduce contaminant concentrations to site-specific remedial goals [40]. Although soil washing is some- times used as a stand-alone treatment technology, more often it is combined with other technologies to complete site remedia- tion. Soil washing technologies have successfully remediated sites contaminated with organic, inorganic, and radioactive con- taminants [40]. The technology does not detoxify or significantly alter the contaminant but transfers the contaminant from the soil into the washing fluid or mechanically concentrates the contami- nants into a much smaller soil mass for subsequent treatment. Further information on soil washing can be found in Innova- tive Site Remediation Technology—Soil Washing/Soil Flushing, Vol. 3, EPA542-B-93-012[41]. Revised versions of an EPAEngi- neering Bulletin and a soil washing treatability study guide are currently in preparation. Process Description—Soil washing systems are quite flex- ible in terms of the number, type, and order of processes in- volved. Soil washing is performed on excavated soil and may involve some or all of the following, depending on the contami- nant-soil matrix characteristics, cleanup goals, and specific pro- cess employed: (1) mechanical screening to remove various over- size materials, (2) crushing to reduce applicable oversize to suit- able dimensions fortreatment; (3) physical processes (e.g. soak- ing, spraying, tumbling, and attrition scrubbing) to liberate weakly bound agglomerates (e.g. silts and clays bound to sand and gravel) followed by size classification to generate coarse-grained and fine-grained soil fraction(s) for further treatment; (4) treat- ment of the coarse-grained soil fraction(s); (5) treatment of the fine-grained fraction(s); and (6) management of the generated residuals. Step 4 above (i.e., treatment of the coarse-grained soil frac- tion) typically involves additional application of physical separa- tion techniques and possibly aqueous-based leaching techniques. Physical separation techniques (e.g., sorting, screening, elutriation, hydrocyclones, spiral concentrators, flotation) exploit physical differences (e.g., size, density, shape, color, wetability) between contaminated particles and soil particles in orderto pro- duce a clean (or nearly clean) coarse fraction and one or more metal-concentrated streams. Many of the physical separation processes listed above involve the use of water as a transport medium, and if the metal contaminant has significant water solu- Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb 11 ------- bility, then some of the coarse-grained soil cleaning will occur as a result of transfer to the aqueous phase. If the combination of physical separation and unaided transfer to the aqueous phase cannot produce the desired reduction in the soil's metal content, which is frequently the case for metal contaminants, then solu- bility enhancement is an option for meeting cleanup goals for the coarse fraction. Solubility enhancement can be accomplished in several ways: (1) converting the contaminant into a more soluble form (e.g., oxidation/reduction, conversion to soluble metal salts); (2) using an aqueous-based leaching solution (e.g., acidic, alka- line, oxidizing, reducing) in which the contaminant has enhanced solubility; (3) incorporating a specific leaching process into the system to promote increased solubilization via increased mix- ing, elevated temperatures, higher solution/soil ratios, efficient solution/soil separation, multiple stage treatment, etc.; or (4) a combination of the above. After the leaching process is com- pleted on the coarse-grained fraction, it will be necessary to sepa- rate the leaching solution and the coarse-grained fraction by settling. A soil rinsing step may be necessary to reduce the re- sidual leachate in the soil to an acceptable level. It may also be necessary to re-adjust soil parameters such as pH or redox po- tential before replacement of the soil on the site. The metal-bear- ing leaching agent must also be treated further to remove the metal contaminant and permit reuse in the process or discharge, and this topic is discussed below under management of residu- als. Treatment of fine-grained soils (Step 5 above) is similar in concept to the treatment of the coarse-grained soils, but the pro- duction rate would be expected to be lower and hence more costly than forthe coarse-grained soil fraction. The reduced pro- duction rate arises from factors including (1) the tendency of clays to agglomerate, thus requiring time, energy, and high water/clay ratios to produce a teachable slurry; and (2) slow settling veloci- ties that require additional time and/or capital equipment to pro- duce acceptable soil/water separation for multi-batch or coun- tercurrent treatment, or at the end of treatment. A site-specific determination needs to be made whether the fines should be treated to produce clean fines orwhetherthey should be handled as a residual waste stream. Management of generated residuals (Step 6 above) is an important aspect of soil washing. The effectiveness, implement- ability, and cost of treating each residual stream is important to the overall success of soil washing forthe site. Perhaps the most important of the residual streams is the metal-loaded leachant that is generated, particularly if the leaching process recycles the leaching solution. Furthermore, it is often critical to the eco- nomic feasibility of the project that the leaching solution be re- cycled. Forthese closed or semi-closed loop leaching processes, successful treatment of the metal-loaded leachant is imperative to the successful cleaning of the soil. The leachant must (1) have adequate solubility forthe metal so that the metal reduction goals can be met without using excessive volumes of leaching solu- tion; and (2) be readily, economically, and repeatedly adjustable (e.g., pH adjustment) to a form in which the metal contaminant has very low solubility so that the recycled aqueous phase re- tains a favorable concentration gradient compared to the con- taminated soil. Also, efficient soil-water separation is important prior to recovering metal from the metal-loaded leachant in or- der to minimize contamination of the metal concentrate. Recy- cling the leachant reduces logistical requirements and costs as- sociated with makeup water, storage, permitting, compliance analyses, and leaching agents. It also reduces external coordi- nation requirements and eliminates the dependence of the re- mediation on the ability to meet Publicly Owned Treatment Works (POTW) discharge requirements. Other residual streams that may be generated and require proper handling include (1) untreatable, uncrushable oversize; (2) recyclable metal-bearing particulates, concentrates, or slud- ges from physical separation or leachate treatment; (3) non-re- cyclable metal-bearing particulates, concentrates, soils, sludges, or organic debris that fail toxicity characteristic leaching proce- dure (TCLP) thresholds for RCRA hazardous waste; (4) soils or sludges that are not RCRA hazardous wastes but are also not sufficiently clean to permit return to the site; (5) metal-loaded leachant from systems where leachant is not recycled; and (6) rinsate from treated soil. Options for residuals treatment are listed in Table 8 at the end of the technology section. Site Requirements—The area required for a unit at a site will depend on the vendor system selected, the amount of soil storage space, and/or the number of tanks or ponds needed for washwater preparation and wastewater storage and treatment. Typical utilities required are water, electricity, steam, and com- pressed air; the quantity of each is vendor- and site-specific. It may be desirable to control the moisture content of the contami- nated soil for consistent handling and treatment by covering the excavation, storage, and treatment areas. Climatic conditions such as annual or seasonal precipitation cause surface runoff and water infiltration; therefore, runoff control measures may be required. Since soil washing is an aqueous based process, cold weather impacts include freezing as well as potential effects on leaching rates. Applicability—Soil washing is potentially applicable to soils contaminated with all five metals of interest. Conditions that par- ticularly favor soil washing include (1) a single principal contami- nant metal that occurs in dense, insoluble particles that report to a specific, small mass fraction(s) of the soil; (2) a single contami- nant metal and species that is very water or aqueous leachant soluble and has a low soil/water partition coefficient; (3) soil con- taining a high proportion (e.g., >80%)of soil particles >2 mm are desirable for efficient contaminant-soil and soil-water separation. Conditions that clearly do not favor soil washing include (1) soils with a high (i.e., >40%) silt and clay fraction; (2) soils that vary widely and frequently in significant characteristics such as soil type, contaminant type and concentration, and where blend- ing for homogeneity is not feasible; (3) complex mixtures (e.g. multicomponent, solid mixtures where access of leaching solu- tions to contaminant is restricted; mixed anionic and cationic met- als where pH of solubility maximums are not close); (4) high clay content, cation exchange capacity, or humic acid content, which would tend to interfere with contaminant desorption; (5) pres- ence of substances that interfere with the leaching solution (e.g., carbonaceous soils would neutralize extracting acids; similarly, high humic acid content will interfere with an alkaline extraction); and (6) metal contaminants in a very low solubility, stable form (e.g., PbS) may require long contact times and excessive amounts of reagent to solubilize. Performance and BOAT Status—Soil washing has been used at waste sites in Europe, especially in Germany, the Neth- erlands, and Belgium [42]. Table 6 lists selected Superfund sites where soil washing has been selected and/or implemented. Acid leaching, which is a form of soil washing, is the BOAT forHg(D009, K071, P065, P092, andU151). SITE Demonstrations and Emerging Technologies Pro- gram Projects—Completed SITE demonstrations applicable to soils contaminated with the metals of interest include • Bergmann USA (Physical separation/leaching) 12 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Table 6. Soil Washing Selections/Applications at Selected Superfund Sites With Metal Contamination Key Metal Site Name/State Specific Technology Contaminants Associated Technology Status3 Ewan Property, NJ GE Wiring Devices, PR King of Prussia, NJ Zanesville Well Field, OH Twin Cities Army Ammunition Plant, MN Sacramento Army Depot Sacramento, CA Water washing Water with Kl solution additive Water with washing agent additives Soil washing Soil washing Soil washing As, Cr, Cu, Pb Hg Ag, Cr, Cu Hg, Pb Cr, Pb Pretreatment by solvent extraction to remove organics Treated residues disposed onsite and covered with clean soil Sludges to be land disposed SVE to remove organics Cd, Cr, Cu, Hg, Pb Soil leaching Offsite disposal of wash liquid S C S/D Status codes as of February 1996: S = selected in ROD; C = completed; S/D = selected, but subsequently de-selected. • BioGenesisSM (Physical separation/leaching) • Biotrol, Inc. (Physical separation) • Brice Environmental Services Corp. (Physical separation) • COGNIS, Inc. (Leaching) « Toronto Harbour Commission (Physical separation/leach- ing) Four SITE Emerging Technologies Program projects have been completed that are applicable to soils contaminated with the metals of interest. Contact—Technology-specific questions regarding soil washing may be directed to Mr. Richard Griffiths at (513) 569- 7832 or Mr. Michael Borst (NRMRL) at (908) 321-6631. Soil Flushing Soil flushing is the in situ extraction of contaminants from the soil via an appropriate washing solution. Water or an aque- ous solution is injected into or sprayed onto the area of contami- nation, and the contaminated elutriate is collected and pumped to the surface for removal, recirculation, or onsite treatment and reinjection. The technology is applicable to both organic and in- organic contaminants, and metals in particular [1], For the pur- pose of metals remediation, soil flushing has been operated at full-scale, but for a small number of sites. Process Description—Soil flushing uses water, a solution of chemicals in water, or an organic extractant to recover con- taminants from the in situ material. The contaminants are mobi- lized by solubilization, formation of emulsions, or a chemical re- action with the flushing solutions. After passing through the con- tamination zone, the contaminant-bearing fluid is collected by strategically placed wells or trenches and brought to the surface for disposal, recirculation, or onsite treatment and reinjection. During elutriation, the flushing solution mobilizes the sorbed con- taminants by dissolution or emulsification. One key to efficient operation of a soil flushing system is the ability to reuse the flushing solution, which is recovered along with groundwater. Various water treatment techniques can be applied to remove the recovered metals and render the extrac- tion fluid suitable for reuse. Recovered flushing fluids may need treatment to meet appropriate discharge standards prior to re- lease to a POTW or receiving waters. The separation of surfac- tants from recovered flushing fluid, for reuse in the process, is a major factor in the cost of soil flushing. Treatment of the flushing fluid results in process sludges and residual solids, such as spent carbon and spent ion exchange resin, which must be appropri- ately treated before disposal. Air emissions of volatile contami- nants from recovered flushing fluids should be collected and treated, as appropriate, to meet applicable regulatory standards. Residual flushing additives in the soil may be a concern and should be evaluated on a site-specific basis [43]. Subsurface con- tainment barriers can be used in conjunction with soil flushing technology to help control the flow of flushing fluids. Further in- formation on soil flushing can be found in the Engineering Bulle- tin: In Situ Soil Flushing [43] or Innovative Site Remediation Tech- nology—Soil Washing/Soil Flushing, Volume 3, EPA 542-B-93- 012 [41]. Site Requirements—Stationary or mobile soil-flushing sys- tems are located onsite. The exact area required will depend on the vendor system selected and the number of tanks or ponds needed for washwater preparation and wastewater treatment. Certain permits may be required for operation, depending on the system being utilized. Slurry walls or other containment struc- tures may be needed along with hydraulic controls to ensure capture of contaminants and flushing additives. Impermeable membranes may be necessary to limit infiltration of precipita- tion, which could cause dilution of the flushing solution and loss of hydraulic control. Cold weather freezing must also be consid- ered for shallow infiltration galleries and above-ground sprayers [44], Applicability—Soil flushing may be easy or difficult to ap- ply, depending on the ability to wet the soil with the flushing solu- tion and to install collection wells or subsurface drains to recover all the applied liquids. The achievable level of treatment varies and depends on the contact of the flushing solution with the con- taminants and the appropriateness of the solution for contami- nants, and the hydraulic conductivity of the soil. Soil flushing is most applicable to contaminants that are relatively soluble in the extracting fluid, and that will not tend to sorb onto soil as the metal-laden flushing fluid proceeds through the soil to the ex- traction point. Based on the earlier discussion of metal behavior, some potentially promising scenarios for soil flushing would in- Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb 13 ------- elude Cr(VI), As (III or V) in permeable soil with low iron oxide, low clay, and high pH; Cd in permeable soil with low clay, low cation exchange capacity (CEC), and moderately acidic pH; and, Pb in acid sands. A single target metal would be preferable to multiple metals, due to the added complexity of selecting a flush- ing fluid that would be reasonably efficient for all contaminants. Also, the flushing fluid must be compatible with not only the con- taminant, but also the soil. Soils that counteract the acidity or alkalinity of the flushing solution will decrease its effectiveness. If precipitants occur due to interaction between the soil and the flushing fluid, then this could obstruct the soil pore structure and inhibit flow to and through sectors of the contaminated soil. It may take long periods of time for soil flushing to achieve cleanup standards. A key advantage of soil flushing is that the contaminant is removed from the soil. Recovery and reuse of the metal from the extraction fluid may be possible in some cases, although the value of the recovered metal would not be expected to fully off- set the costs of recovery. The equipment used for the technol- ogy is relatively easy to construct and operate. It does not in- volve excavation, treatment, and disposal of the soil, which avoids the expense and hazards associated with these activities. Performance and BOAT Status—Table 7 lists the Super- fund sites where soil flushing has been selected and/or imple- mented. Soil flushing has a more established history for removal of organics but has been used for Cr removal (e.g., United Chrome Products Superfund Site, near Corvallis, Oregon). In situ technologies, such as soil flushing, are not considered RCRA BOAT for any of the five metals. Soil flushing techniques for mobilizing contaminants can be classified as conventional and unconventional. Conventional applications employ water only as the flushing solution. Uncon- ventional applications that are currently being researched in- clude the enhancement of the flushing water with additives, such as acids, bases, and chelating agents to aid in the desorption/ dissolution of the target contaminants from the soil matrix to which they are bound. Researchers are also investigating the effects of numerous soil factors on heavy metal sorption and migration in the sub- surface. Such factors include pH, soil type, soil horizon, CEC, particle size, permeability, specific metal type and concentra- tion, and type and concentrations of organic and inorganic com- pounds in solutions. Generally, as the soil pH decreases, cat- ionic metal solubility and mobility increase. In most cases, metal mobility and sorption are likely to be controlled by the organic fraction in topsoils, and clay content in the subsoils. SITE Demonstration and Emerging Technologies Pro- gram Projects—There are no in situ soil flushing projects re- ported to be completed or ongoing either as SITE demonstra- tion or Emerging Technologies Program Projects [44]. Contact—Technology-specific questions regarding soil flushing may be directed to Mr. Jerry N. Jones (NRMRL) at (405) 436-8593. Pyrometallurgy is used here as a broad term encompass- ing elevated temperature techniques for extraction and process- ing of metals for use or disposal. High-temperature processing increases the rate of reaction and often makes the reaction equi- librium more favorable, lowering the required reactor volume per unit output [1]. Some processes that clearly involve both metal extraction and recovery include roasting, retorting, or smelting. While these processes typically produce a metal-bearing waste slag, metal is also recovered for reuse. A second class of pyro- metallurgical technologies included here is a combination of high temperature extraction and immobilization. These processes use thermal means to cause volatile metals to separate from the soil and report to the fly ash, but the metal in the fly ash is then immobilized, instead of recovered, and there is no metal recov- ered for reuse. A third class of technologies are those that are primarily incinerators for mixed organic-inorganic wastes, but which have the capability of processing wastes containing the metals of interest by either capturing volatile metals in the ex- haust gases or immobilizing the nonvolatile metals in the bottom ash or slag. As noted in the introduction, mixed organic-metal waste is beyond the scope of this bulletin. However, since some of these systems may have applicability to some cases where metals contamination is the primary concern, a few technolo- gies of this type are noted that are in the SITE program. Vitrifica- tion is addressed in a previous section. It is not considered pyro- metallurgical treatment since there is typically neither a metal extraction nor a metal recovery component in the process. Process Description—Pyrometallurgical processing usu- ally is preceded by physical treatment to produce a uniform feed material and upgrade the metal content. Solids treatment in a high-temperature furnace requires ef- ficient heat transfer between the gas and solid phases while mini- mizing particulate in the off-gas. The particle-size range that meets these objectives is limited and is specific to the design of the process. The presence of large clumps or debris slows heat transfer, so pretreatment to either remove or pulverize oversize material normally is required. Fine particles also are undesir- able because they become entrained in the gas flow, increasing the volume of dust to be removed from the flue gas. The feed material is sometimes pelletized to give a uniform size. In many cases a reducing agent and flux may be mixed in prior to pallati- zation to ensure good contact between the treatment agents and the contaminated material and to improve gas flow in the reactor [1]- Table 7. Soil Flushing Selections/Applications at Selected Superfund Sites With Metal Contamination Key Metal Site Name/State Specific Technology Contaminants Associated Technology Status3 Lipari Landfill, NJ United Chrome Products, OR Soil flushing of soil and wastes Cr, Hg, Pb contained by slurry wall and cap; excavation from impacted wetlands Soil flushing with water Cr Slurry wall and cap Electrokinetic Pilot test, Considering in situ reduction I ' Status codes as of February 1996: I = in operation, not complete. 14 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Due to its relatively low boiling point (357°C) and ready con- version at elevated temperature to its metallic form, Hg is com- monly recovered through roasting and retorting at much lower temperatures than the other metals. Pyrometallurgical process- ing to convert compounds of the other four metals to elemental metal requires a reducing agent, fluxing agents to facilitate melt- ing and to slag off impurities, and a heat source. The fluid mass often is called a melt, but the operating temperature, although quite high, often is still below the melting points of the refractory compounds being processed. The fluid forms as a lower-melt- ing-point material due to the presence of a fluxing agent such as calcium. Depending on processing temperatures, volatile metals such as Cd and Pb may fume off and be recovered from the off- gas as oxides. Nonvolatile metals, such as Cr or nickel, are tapped from the furnace as molten metal. Impurities are scavenged by formation of slag [1]. The effluents and solid products generated by pyrometallurgical technologies typically include solid, liquid, and gaseous residuals. Solid products include debris, oversized rejects, dust, ash, and the treated medium. Dust collected from particulate control devices may be combined with the treated medium or, depending on analyses for carryover contamination, recycled through the treatment unit. Site Requirements—Few pyrometallurgical systems are currently available in mobile or transportable configurations. Since this is typically an off-site technology, the distance of the site from the processing facility has an important influence on trans- portation costs. Off-site treatment must comply with EPA's off- site treatment policies and procedures. The off-site facility's en- vironmental compliance status must be acceptable, and the waste must be of a type allowable under their operating permits. In order for pyrometallurgical processing to be technically feasible, it must be possible to generate a concentrate from the contami- nated soil that will be acceptable to the processor. The process- ing rate of the off-site facility must be adequate to treat the con- taminated material in a reasonable amount of time. Storage re- quirements and responsibilities must be determined. The need for air discharge and other permits must be determined on a site specific basis. Applicability—With the possible exception of Hg, or a highly-contaminated soil, pyrometallurgical processing where metal recovery is the goal would not be applied directly to the contaminated soil, but rather to a concentrate generated via soil washing. Pyrometallurgical processing in conventional rotary kilns, rotary furnaces, or arc furnaces is most likely to be appli- cable to large volumes of material containing metal concentra- tions (particularly, Pb, Cd, or Cr) higher than 5 to 20%. Unless a very concentrated feed stream can be generated (e.g., approxi- mately 60% for Pb), there will be a charge, in addition to trans- portation, for processing the concentrate. Lower metal concen- trations can be acceptable if the metal is particularly easy to reduce and vaporize (e.g., Hg) or is particularly valuable (e.g., gold or platinum). As is the weakest candidate for pyrometallur- gical recovery, since there is almost no recycling of As in the U.S. As [$250 to $500 per metric ton (mt)] for As trioxide) is also the least valuable of the metals. The reported price range [1] for the other metals are Cd ($5,950/mt); Cr ($7,830/mt); Pb ($700 to $770/mt); and, Hg ($5,295 to $8,490/mt). Performance and BOAT Status—The technical resource document (1) contains a list of approximately 35 facilities/ad- dresses/contacts that may accept concentrates of the five met- als of interest for pyrometallurgical processing. Sixteen of the 35 facilities are Pb recycling operations, 7 facilities recover Hg, and the remainder address a range of RCRA wastes that contain the metals of interest. Due to the large volume of electric arc furnace (EAF) emission control waste (K061), extensive processing ca- pability has been developed to recover Cd, Pb, and zinc from solid waste matrices. Permitting is being expanded to cover other hazardous waste types. The currently available process tech- nologies for K061 and similar materials include • Waelz kiln process (Horsehead Resource Development Company, Inc.) • Waelz kiln and calcination process (Horsehead Resource Development Company, Inc.) • Flame reactor process (Horsehead Resource Develop- ment Company, Inc.) • Inclined rotary kiln (Zia Technology) Plasma arc furnaces currently are successfully treating K061 (EAF waste) at two steel plants. These are site-dedicated units that do not accept outside material for processing. Pyrometallurgical recovery is a BOAT forthe following waste types: • Cd-containing batteries, D006 • Pb nonwastewaters such as K069 in the noncalcium sul- fate subcategory • Hg wastes, P065, P092, and D009 (organics) prior to re- torting [45] • Pb acid batteries such as D008 • Zinc nonwastewaters such as K061 in the high zinc sub- category • Hg from wastewater treatment sludge such as K106 in the high-Hg subcategory • Hg such as U151 in the high-Hg subcategory. SITE Demonstration and Emerging Technologies Pro- gram Projects—Completed SITE demonstrations applicable to soils contaminated with the metals of interest include • RUST Remedial Services, Inc. (X-Trax Thermal Desorp- tion) • Horsehead Resource Development Company, Inc. (Flame Reactor) Four SITE Emerging Technology Program projects that are applicable to the metals of interest have been completed or are ongoing. Contact—Technology-specific questions regarding pyromet- allurgical treatment may be directed to Mrs. Marta K. Richards (NRMRL) at (513) 569-7692. of Trains Several of the metal remediation technologies discussed are often enhanced through the use of treatment trains. Treatment trains use two or more remedial options applied sequentially to the contaminated soil and often increase the effectiveness while decreasing the cost of remediation. Processes involved in treat- ment trains include soil pretreatment, physical separation de- signed to decrease the amount of soil requiring treatment, addi- tional treatment of process residuals or off-gases, and a variety of other physical and chemical techniques, which can greatly Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb 15 ------- Table 8 Typical Treatment Trains Contain- Vitrifi- Soil Pyromet- Soil ment S/Sa cation3 Washing allurgical Flushing Pretreatment Excavation • E,P I,E Debris removal E,P E Oversize reduction E,P E Adjust pH • I,E,P Reduction [e.g., Cr(VI) to Cr(lll)] • I,E Oxidation [e.g., As(lll) to As (V)] • I,E Treatment to remove or destroy organics I,E Physical separation of rich and lean fractions I,E,P E Dewatering and drying for wet sludge P E Conversion of metals to less volatile forms [e.g.,As203toCa3(As04)2] E Addition of high temperature reductants Pelletizing Flushing fluid delivery and extraction system Containment barriers • I.E.P I Post-treatment/Residuals Management Disposal of treated solid residuals (preferably below the frost line and above the water table) I.E.P E Containment barriers I,E,P I,E Off-gas treatment I,E,P I,E Reuse for onsite paving P Metal recovery from extraction fluid by aqueous processing (ion exchange, electrowinning, etc.) Pyrometallurgical recovery of metal from sludge Processing and reuse of leaching solution S/S treatment of leached residual Disposal of solid process residuals (preferably below the frostline and above the water table) Disposal of liquid process residuals S/S treatment of slag or fly ash Reuse of slag/vitreous product as construction material E Reuse of metal or metal compound Further processing of metal or metal compound Flushing liquid/groundwater treatment/disposal • a Technology has been divided into the following categories: I = In Situ Process; E = Ex Situ Process; P= Polymer Microencapsulation (Ex Situ) improve the performance of the remediation technology. Table 8 onstration Reports, and EPA electronic databases. The reader is provides examples of treatment trains used to enhance each cautioned that the cost estimates generally do not include pre- metal remediation technology that has been discussed. treatment, site preparation, regulatory compliance costs, costs for additional treatment of process residuals (e.g., stabilization Cost Ranges Of Remedial Technologies of incinerator ash or disposal of metals concentrated by solvent extraction), or profit. Since the actual cost of employing a reme- Estimated cost ranges for the basic operation of the tech- dial technology at a specific site may be significantly different nology are presented in Figure 1. The information was compiled than these estimates, data are best used for order-of-magnitude from EPAdocuments, including Engineering Bulletins, SITE Dem- cos^ evaluations. 16 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- Containment3 S/S Vitrification Soil Washing Soil Flushing11 Pyrometallurgical 10 to 90 -> 60 to 290 -> 400 to 870 -> 60 to 245 60 to 163 250 to 560 0 100 200 300 400 500 600 Cost ($/ton) 3 Includes landfill caps and slurry walls. A slurry wall depth of 20' is assumed. b Costs reported in $/Yd3, assumed soil density of 100 Ib/ft3 700 800 900 1000 Figure 1. Estimated Cost Ranges of Metals Remediation Technologies [Source: VISIT! (Ver. 3.0), various EPA Engineering Bulletins and TRD of Additional Information The following databases, reports, and EPA hotlines offer ad- ditional information on the remediation of metal-contaminated soil. The reader is also encouraged to review sources referenced in this paper. Alternative Treatment Technology Information Center(AT- TIC) database. U.S. EPAAssistance, (908)321-6677. AT- TIC modem contact, (703) 908-2138 (1200 or2400 baud), and the modem settings are no parity, 8 data bits, 1 stop bit, and full duplex. The Clean-Up Information Bulletin Board System (CLU- IN). System Operator, (301) 589-8368. Online communi- cation, (301)589-8366. EPA Online Library System (OLS). Includes the following applicable databases: The National Catalog, The Haz- ardous Waste Superfund Data Collection, and The Chemi- cal Collection System. Online communication, (919) 549- 0720. Public Information Center, (202) 260-2080. Records of Decision System (RODS) database. RODS staff and registration, (703)603-9091. RODS database searches, (703) 538-7234. Subsurface Remediation Technology (SRT) Database. Database information, contact Dr. David S. Burden, (405) 436-8606. Cost of Remedial Action (CORA). PC-based database available on disk. Hazardous Waste Superfund Data Collection (HWSDC). PC-based database available on disk. For information, Felice Sacks, (202) 260-3121. Risk Reduction Engineering Laboratory (RREL)Treatabil- ity Database. Available on disk and through the ATTIC database. Contact Glenn Shaul, (513) 569-7589. Vendor Information System for Innovative Treatment Tech- nologies (VISITT) database. PC-based database avail- able on disk, (800) 245-4505 or (703) 883-8448. ReOpt/Remedial Action Assessment System (RAAS) da- tabases. U.S. Department of Energy. For government projects only-a contract number must be filed with PNL for each copy received. EPA Home Page on World Wide Web (http://www. epa.gov). Marks, Peter J., Walter J. Wujcik, and Amy F. Loncar. Re- mediation Technologies Screening Matrix and Reference Guide, Second Edition. U.S. Army Environmental Center. October 1994. RCRA/Superfund Assistance Hotline. Washington, D.C., (800) 424-9346. U.S. Environmental Protection Agency. Lining of Waste Containment and Other Impoundment Facilities, EPA/600/ 2-88-052. 1988. U.S. Environmental Protection Agency. Design, Construc- tion, and Evaluation of Clay Liners for Waste Manage- ment Facilities, EPA/530/SW-86/007F. November 1988. U.S. Environmental Protection Agency. Technical Guid- ance Document: Final Covers on Hazardous Waste Land- fills and Surface Impoundments, EPA/530-SW-89-047. July 1989. U.S. Environmental Protection Agency. Technical Guid- ance Document: Inspection Techniques for the Fabrica- Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb 17 ------- tion of Geomembrane Field Seams, EPA/530/SW-91/051. May 1991 U.S. Environmental Protection Agency. Technical Guid- ance Document: Construction Quality Management for Remedial Action and Remedial Design Waste Contain- ment Systems, EPA/540/R-92/Q73. October 1992. U.S. Environmental Protection Agency. Technical Guid- ance Document: Quality Assurance and Quality Control for Waste Containment Facilities, EPA/600/R-93/182. 1993. Acknowledgments This Engineering Bulletin was prepared by the U.S. Envi- ronmental Protection Agency, Office of Research and Develop- ment (ORD), National Risk Management Research Laboratory (NRMRL), Edison, New Jersey, with the assistance of Science Applications International Corporation (SAIC) under Contract No. 68-C5-0001. Mr. Michael D. Royer served as the EPA Technical Project Manager. Ms. Margaret Groeber was the SAIC WorkAs- signment Manager and author. The author is especially grateful to George Wahl, Joe Tillman, and Kristin Meyer of SAIC, who contributed significantly to the development of this document. The following EPA personnel have contributed their time and comments by participating in peer reviews of sections of the document: Edwin Barth, NRMRL-Ci Edward Bates, NRMRL-Ci Benjamin Blaney, NRMRL-Ci Michael Borst, NRMRL-Edison David Burden, NRMRL-Ada David Carson, NRMRL-Ci Harry Compton, ERT, OSWER Patricia Erickson, NRMRL-Ci Frank J. Freestone, NRMRL-Edison Richard Griffiths, NRMRL-Ci Jerry N. Jones, NRMRL-Ada Richard Koustas, NRMRL-Edison Norm Kulujian, ORD-Region III Ann Leitzinger, NRMRL-Ci Shaun McGarvey, OSWER Robert Puls, NRMRL-Ada Marta Richards, NRMRL-Ci Teri Richardson, NRMRL-Ci Larry Rosengrant, OWSER James Ryan, NRMRL-Ci Robert Stamnes, Region X Mary Stinson, NRMRL-Edison Andre Zownir, ERT, OSWER REFERENCES 1. USEPA. Contaminants and Remedial Options at Selected Metal-Contaminated Sites, EPA/540/R-95/512. Washing- ton, DC: U.S. Environmental Protection Agency, Office of Research and Development, July 1995. 2. USEPA. In Situ Technologies for the Remediation of Soils Contaminated with Metals—Status Report (Draft). U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Technology Innovation Office (In Progress, 7/96). 3. USEPA. Selection of Control Technologies for Remedia- tion of Lead Battery Recycling Sites, EPA/540/2-91/014. U.S. Environmental Protection Agency, 1991. 4. USEPA. Engineering Bulletin: Selection of Control Tech- nologies for Remediation of Lead Battery Recycling Sites, EPA/540/S-92/011. Cincinnati, OH: U.S. Environmental Protection Agency, 1992. 5. USEPA. Contaminants and Remedial Options at Wood Preserving Sites, EPA600/R-92/182. Washington, DC: U.S. Environmental Protection Agency, Office of Research and Development, 1992. 6. USEPA. Presumptive Remedies for Soils, Sediments, and Sludges at Wood Treater Sites, EPA/540/R-95/128. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, 1995. 7. USEPA. Contaminants and Remedial Options at Pesti- cide Sites, EPA/600/R-94/202. Washington, DC: U.S. En- vironmental Protection Agency, Office of Research and Development, 1994. 8. USEPA. Separation/Concentration Technology Alterna- tives for the Remediation of Pesticide-Contaminated Soil, EPA/540/S-97/503. Washington, DC: U.S. Environmental Protection Agency, Office of Emergency and Remedial Response, and Office of Research and Development, 1997. 9. McLean, J.E. and B.E. Bledsoe. Behavior of Metals in Soils, EPA/540/S-92/018. Washington, DC: U.S. Environ- mental Protection Agency, Office of Solid Waste and Emergency Response, and Office of Research and De- velopment, 1992. 18 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- 10. Palmer, C.D. and R.W. Puls. Natural Attenuation of Hexavalent Chromium in Ground Water and Soils, EPA/ 540/S-94/505. Washington, DC: U.S. Environmental Pro- tection Agency, Office of Solid Waste and Emergency Response, and Office of Research and Development, 1994. 11. Benjamin, M.M. and J.D. Leckie. Adsorption of Metals at Oxide Interfaces: Effects of the Concentrations of Adsor- bate and Competing Metals. Chapter 16 in Contaminants and Sediments, Volume 2: Analysis, Chemistry, Biology, Edited by R.A. Baker, Ann Arbor, Ml: Ann Arbor Science Publishers, Inc., 1980. 12. Wagemann, R. Some Theoretical Aspects of Stability and Solubility of Inorganic As in the Freshwater Environment. Water Research 12:139-145 (1978). 13. Zimmerman, L. and C. Coles. "Cement Industry Solutions to Waste Management—The Utilization of Processed Waste By-Products for Cement-Manufacturing". In Pro- ceedings of the 1st International Conference for Cement Industry Solutions to Waste Management, Calgary, Alberta, Canada, 1992, 533-545. 14. Roy F. Weston. Installation Restoration General Environ- mental Technology Development Guidelines forln-Place Closure of Dry Lagoons. U.S. Army Toxic and Hazardous Materials, May 1985. 15. USEPA. Slurry Trench Construction for Pollution Migra- tion Control, EPA/540/2-84/001. Washington, DC: U.S. En- vironmental Protection Agency, Office of Emergency and Remedial Response, February 1984. 16. USEPA. Grouting Techniques in Bottom Sealing of Haz- ardous Waste Sites, EPA/600/2-86/020. U.S. Environmen- tal Protection Agency, 1986. 17. USEPA. Engineering Bulletin: Slurry Walls, EPA/540/S- 92/008. Cincinnati, OH: U.S. Environmental Protection Agency, Office of Research and Development, October 1992. 18. USEPA. Engineering Bulletin: Landfill Covers, EPA/540/ S-93/5QO. Cincinnati, OH: U.S. Environmental Protection Agency, Office of Research and Development, February 1993. 19. USEPA. Technical Resource Document: Solidification/Sta- bilization and Its Application to Waste Materials, EPA/530/ R-93/012. Cincinnati, OH: U.S. Environmental Protection Agency, Risk Reduction Engineering Laboratory, Office of Research and Development, June 1993. 20. USEPA. Engineering Bulletin: Solidification/Stabilization ofOrganics and Inorganics, EPA/540/S-92/015. Cincin- nati, OH: U.S. Environmental Protection Agency, Office of Research and Development, 1992. 21. Conner, J.R. Chemical Fixation and Solidification of Haz- ardous Wastes. VanNostrand Reinhold, New York, NY, 1990. 22. Anderson, William C., Ed. Innovative Site Remediation Technology: Solidification/Stabilization, Volume 4. WASTECH, American Academy of Environmental Engi- neers, June 1994. Note: EPA printed under license (No. EPA/542-B-94-001). 23. USEPA. Handbook on In Situ Treatment of Hazardous Waste-Contaminated Soils, EPA/540/2-90/002. Cincinnati, OH: U.S. Environmental Protection Agency, Risk Reduc- tion Engineering Laboratory, 1990. 24. Arniella, E.F. and L.J. Blythe. Solidifying Traps Hazard- ous Waste. Chemical Engineering 97(2):92-102, 1990. 25. Kalb, P.O., H.H. Burns, and M. Meyer. "Thermo-plastic En- capsulation Treatability Study for a Mixed Waste Incin- erator Off-Gas Scrubbing Solution." InT.M. Gilliam(Ed.), Third International Symposium on Stabilization /Solidifi- cation of Hazardous, Radioactive, and Mixed Wastes, ASTM STP 1240, American Society for Testing and Ma- terials, Philadelphia, Pennsylvania, 1993. 26. Ponder, T.G. and D. Schmitt. "Field Assessment of Air Emission from Hazardous Waste Stabilization Operation." In Proceedings of the 17th Annual Hazardous Waste Research Symposium, EPA/600/9-91/002, Cincinnati, OH, 1991. 27. Shukla, S.S. and A.S. Shukla, and K.C. Lee. Solid-ification/ Stabilization Study for the Disposal of Pentachlorophe- nol. Journal of Hazardous Materials 30:317-331, 1992. 28. USEPA. Evaluation of Solidification/Stabilization as a Best Demonstrated Available Technology for Contaminated Soils, EPA/600/2-89/013. Cincinnati, OH: U.S. Environ- mental Protection Agency, Risk Reduction Engineering Laboratory, 1989. 29. Weitzman, L. and L.E. Hamel. "Volatile Emissions from Stabilized Waste." In Proceedings of the 15th Annual Re- search Symposium, EPA/600/9-90/006, U.S. Environmen- tal Protection Agency, Cincinnati, OH, 1990. 30. Means, J.L, K.W Nehring, and J.C. Heath. "Abrasive Blast Material Utilization in Asphalt Roadbed Material." Third International Symposium on Stabilization/Solidification of Hazardous, Radioactive, and Mixed Wastes, ASTM STP 1240, American Society for Testing and Materials, Phila- delphia, Pennsylvania, 1993. 31. Buelt, J.L., C.L. Timmerman, K.H. Oma, V.F. FitzPatrick, and J.G. Carter. In Situ Vitrification ofTransuranic Waste: An Updated Systems Evaluation and Applications As- sessment, PNL-4800. Richland, WA: Pacific Northwest Laboratory, 1987. 32. USEPA. Vitrification Technologies for Treatment of Haz- ardous and Radioactive Waste, EPA/625/R-92/002. Cin- cinnati, OH: U.S. Environmental Protection Agency, May 1992. 33. USEPA. Engineering Bulletin-In Situ Vitrification Treat- ment, EPA/540/S-94/504. Cincinnati, OH: U.S. Environ- mental Protection Agency, Office of Research and De- velopment, October 1994. 34. FitzPatrick, V.F., C.L. Timmerman, and J.L. Buelt. "In Situ Vitrification: An Innovative Thermal Treatment Technol- ogy." In Proceedings of the Second International Confer- ence on New Frontiers for Hazardous Waste Manage- ment, EPA/600/9-87/018F. U.S. Environmental Protection Agency, 1987,305-322. Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb 19 ------- 35. Tim merman, C.L. In Situ Vitrification of PCS Contami- nated Soils, EPRI CS-4839. Palo Alto, CA: Electric Power Research Institute, 1986. 36. USEPA. The Superfund innovative Technology Evalua- tion Program: Technology Profiles, Fourth Edition, EPA/ 540/5-91/008. Washington, DC: U.S. Environmental Pro- tection Agency, Office of Solid Waste and Emergency Response, 1991. 37. USEPA. Geosafe Corporation In Situ Vitrification Innova- tive Technology Evaluation Report, EPA/540/R-94/520. Washington, DC: U.S. Environmental Protection Agency, Office of Research and Development, March 1995. 38. Luey, J., S.S. Koegler, W.L. Kuhn, P.S. Lowery, and R.G. Winkelman. In Situ Vitrification of a Mixed-Waste Con- taminated Soil Site: The 116-B-6ACribatHanford, PNL- 8281. Richland, WA: Pacific Northwest Laboratory, 1992. 39. Hansen, J.E. and V.F. FitzPatrick. In Situ Vitrification Ap- plications. Richland, WA: Geosafe Corporation, 1991. 40.USEPA. Engineering Bulletin: Soil Washing Treatment, EPA/540/2-90/017. Cincinnati, OH: U.S. Environmental Protection Agency, Office of Research and Development, (currently being revised 1996). 41. William C. Anderson, Editor. Innovative Site Remediation Technology: Soil Washing/Flushing, Volume 3. American Academy of Environmental Engineers, November 1993. Note: Published by EPA under EPA542-B-93-012. 42. USEPA. Citizens Guide to Soil Washing, EPA/542/F-92/ 003. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, March 1992. 43. USEPA. Engineering Bulletin: In Situ Soil Flushing, EPA/ 540/2-91/021. Cincinnati, OH: U.S. Environ-mental Pro- tection Agency, Office of Research and Development, Oc- tober 1991. 44. USEPA. Superfund Innovative Technology Evaluation Pro- gram: Technology Profiles, 7th Edition, EPA/540/R-94/526. Washington, DC: U.S. Environmental Protection Agency, Office of Research and Development, November 1994. 45. 55 Fed. Reg. 22572 (June 1, 1990). 20 Technology Alternatives for Remediation of Soils Contaminated with As, Cd, Cr, Hg & Pb ------- |