Best Demonstrated Available Technology BDAT Background Document For Aniline Production Group k103 K104 Volume 7

United States Office of EPA/530-SW-88-0009-g EPA/530-SW-88-OOUyg Environmental Protection SolidWaste Apnl1988 Agency Washington, D.C. 20460 Solid Waste 4>EPA Best Proposed MIVIRONMENTA* PROTECTION Available Technology AGENCY ^MUtAs- TEXAC (BDAT) Background Document for Aniline Production Treatability Group (K103, K104) Volume 7 ------- FINAL BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT) BACKGROUND DOCUMENT FOR K103 AND K104 Volume 7 U. S. Environmental Protection Agency Office of Solid Waste 401 M Street, S.W. Washington, D.C. 20460 James R. Berlow, Chief Treatment Technology Section April 1988 ------- BOAT BACKGROUND DOCUMENT FOR K103 and K104 TABLE OF CONTENTS VOLUME 7 Page Executive Summary i BOAT Treatment Standards for K103 and K104 vii SECTION 1. Introduction 1-1 SECTION 2. Industries Affected and Waste Characterization 2-1 SECTION 3. Demonstrated/Applicable Treatment Technologies 3-1 SECTION 4. Selection of BOAT 4-1 SECTION 5. Determination of Regulated Constituents . . . 5-1 SECTION 6. Calculation of Treatment Standard 6-1 SECTION 7. Conclusions 7-1 APPENDIX A Statistical Analysis A-l APPENDIX B Analysis of Variance Tests B-l APPENDIX C Detection Limits for Constituents in the Untreated and Treated Waste C-l APPENDIX D Calculation of Treatment Standards D-l APPENDIX E Analytical QA/QC E-l APPENDIX F Thermal Conductivity Summary F-l Rev. 3 ------- EXECUTIVE SUMMARY BOAT Treatment Standards for K103 and K104 Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted on November 8, 1984, and in accordance with the procedures for establishing treatment standards under section 3004 (m) of the Resource Conservation and Recovery Act (RCRA), the Environmental Protection Agency (EPA) is proposing treatment standards for the listed wastes, K103 and K104, based on the performance of treatment technologies determined by the Agency to represent Best Demonstrated Available Technology (BOAT). This background document provides the detailed analyses that support this determination. These BDAT treatment standards represent maximum acceptable concentration levels for selected hazardous constituents in the wastes or residuals from treatment and/or recycling. These levels are established as a prerequisite for disposal of these wastes in units designated as land disposal units according to 40 CFR 268 (Code of Federal Regulations). Wastes which, as generated, contain the regulated constituents at concentrations which do not exceed the treatment standards are not restricted from land disposal units. The Agency has chosen to set levels for these wastes rather than designating the use of a specific treatment technology. The Agency believes that this allows the Rev. 3 ------- generators of these wastes a greater degree of flexibility in selecting a technology or train of technologies that can achieve these levels. These standards become effective as of August 8, 1988, as described in the schedule set forth in 40 CFR 268.10. According to 40 CFR 261.32 (hazardous wastes from specific sources) waste codes K103 and K104 are from the nitrobenzene/aniline industry and are listed as follows: K103: Process residues from aniline extraction from the production of aniline. K104: Combined wastewater streams generated from nitrobenzene/aniline production. Descriptions of the industry and specific processes generating these wastes, as well as descriptions of the physical and chemical waste characteristics, are provided in Section 2.0 of this document. The four digit Standard Industrial Classification (SIC) code most often reported for the industry generating this waste code is 2869 (nitrobenzene/aniline). The Agency estimates that there are six facilities that may potentially generate wastes identified as K103-K104. The Agency has determined that K103/K104 collectively represent one general treatability group with two subgroups - y wastewaters and nonwastewaters. For the purpose of the land disposal restrictions rule, wastewaters are defined as wastes containing less than 1% (weight basis) filterable solids and less ii Rev. 3 ------- than 1% (weight basis) total organic carbon (TOC). For K103 and K104 wastes, this definition was amended to include wastewaters with a TOC content up to 4% (weight basis). Wastes not meeting this definition are classified as nonwastewaters. These treatability subgroups represent classes of wastes that have similar physical and chemical properties within each subgroup. EPA believes that each waste within these subgroups can be treated to the same concentrations when similar technologies are applied. The Agency has examined the sources of these two wastes from the nitrobenzene/aniline industry, the specific similarities in waste composition, potential applicable and demonstrated technologies, and attainable treatment performance in order to support a simplified regulatory approach. While the Agency has not, at this time, specifically identified additional wastes which would fall into this treatability group or two subgroups, this does not preclude the Agency from extrapolating these standards to other wastes, in the future. The K103 and K104 wastes, as generated, have a high water content and are typically classified as wastewaters. Residues from the treatment of these wastewaters (such as spent carbon and the nitrobenzene solvent stream from the nitrobenzene * liquid/liquid extractor) are classified as nonwastewaters. The K103/K104 nonwastewaters are generated primarily as a result of the "derived-from rule" and the "mixture-rule" as outlined in 40 iii Rev. 3 ------- CFR 261.3 (definition of hazardous waste). The Agency has proposed BOAT treatment standards for the two treatability subgroups of the K103 and K104 wastes - wastewaters and nonwastewaters. In general, these treatment standards have been proposed for a total of five (5) organic constituents. In addition, a treatment standard has been proposed for one (1) inorganic constituent in K104. The organic constituents that are proposed for regulation in K103 and K104 wastes codes are as follows: benzene, aniline, 2,4-dinitrophenol, nitrobenzene, and phenol. Total cyanides were also proposed for regulation in K104. Sulfide was not proposed for regulation in K103 because the Agency requires additional analytical data on sulfide to determine if it was effectively treated by the treatment system. A detailed discussion of the selection of constituents to be regulated is presented in Section 5.0 of this document. BOAT treatment standards for wastewater K103 and K104 are proposed based on performance data from a treatment train which consisted of liquid/liquid extraction followed by steam stripping and activated carbon adsorption. Testing was performed on representative samples of K103 and K104. Liquid/liquid extraction followed by steam stripping and activated carbon v adsorption was determined to represent the best demonstrated available technology (BOAT). This determination was based on a statistical comparison of performance data. The Agency collected iv Rev. 3 ------- performance data for a treatment train consisting of liquid/liquid extraction followed by steam stripping and carbon adsorption. A statistical comparison was done with this performance data from liquid/liquid extraction followed by steam stripping and from liquid/liquid extraction alone. Based on this analysis, the Agency has determined that the data for liquid/liquid extraction followed by steam stripping and activated carbon adsorption indicated the highest level of performance. BOAT treatment standards for K103 and K104 nonwastewaters are proposed based on a transfer of treatment standards developed for K048/K051 nonwastewaters (dissolved air flotation float and API separator sludge from the petroleum industry). These standards were developed based on the incineration of K048/K051 nonwastewaters. Treatment data were transferred on a constituent basis from either the same constituent or from constituents judged to be similar in physical and chemical properties. A detailed discussion of the transfer of the data and methodology is presented in Section 6.0 of this document. The following tables list the specific BDAT treatment standards for wastes identified as K103 and K104. The Agency is * setting standards based on analyses of total composition for both wastewater and nonwastewater forms of K103 and K104. The units for total composition analysis are in parts per million (mg/kg) Rev. 3 ------- on a weight by weight basis for nonwastewaters. For wastewaters the units are expressed on a weight per unit volume basis (mg/1). Testing procedures are specifically identified in the quality assurance sections of this document. vi Rev. 3 ------- BOAT TREATMENT STANDARDS FOR K103/K104 WASTES WASTEWATER Regulated Constituents Total Composition (mg/1) K103 K104 Benzene Aniline 2 , 4-Dinitrophenol Nitrobenzene Phenol Total Cyanides (CN) 0.147 4.450 0.613 0.073 1.391 NR 0.147 4.450 0.613 0.073 1.391 2.683 NR = Not regulated since it is not presented at treatable levels. NONWASTEWATER (Nonwastewater forms of K103/K104 represent spent carbon from the activated carbon adsorber. Treatment standards were transferred from K019 for benzene, aniline, 2,4-dinitrophenol, nitrobenzene, and phenol and from K048/K051 for total cyanides). Regulated Constituents Total Composition (mg/kg) K103 K104 Benzene Aniline 2 , 4-Dinitrophenol Nitrobenzene Phenol Total Cyanides (CN) 5.96 5.44 5.44 5.44 5.44 . NR 5.96 5.44 5.44 5.44 5.44 1.48 NR = Not regulated since it is not present at treatable levels, VII Rev. 3 ------- 1. INTRODUCTION This section of the background document presents a summary of the legal authority pursuant to which the BDAT treatment standards were developed, a summary of EPA's promulgated methodology for developing BDAT, and finally a discussion of the petition process that should be followed to request a variance from the BDAT treatment standards. 1.1 Legal Background 1.1.1 Requirements Under HSWA The Hazardous and Solid Waste Amendments of 1984 (HSWA), enacted on November 8, 1984, and which amended the Resource Conservation and Recovery Act of 1976 (RCRA), impose substantial new responsibilities on those who handle hazardous waste. In particular, the amendments require the Agency to promulgate regulations that restrict the land disposal of untreated hazardous wastes. In its enactment of HSWA, Congress stated explicitly that "reliance on land disposal should be minimized or eliminated, and land disposal, particularly landfill and surface impoundment, should be the least favored method for managing hazardous wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)). 1-1 Rev. 3 ------- One part of the amendments specifies dates on which particular groups of untreated hazardous wastes will be prohibited from land disposal unless "it has been demonstrated to the Administrator, to a reasonable degree of certainty, that there will be no migration of hazardous constituents from the disposal unit or injection zone for as long as the wastes remain hazardous" (RCRA section 3004(d)(l), (e) (1) , (g) (5) , 42 U.S.C. 6924 For the purpose of the restrictions, HSWA defines land disposal "to include, but not be limited to, any placement of ... hazardous waste in a landfill, surface impoundment, waste pile, injection well, land treatment facility, salt dome formation, salt bed formation, or underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924 (k)). Although HSWA defines land disposal to include injection wells, such disposal of solvents, dioxins, and certain other wastes, known as the California List wastes, is covered on a separate schedule (RCRA section 3004 (f) (2), 42 U.S.C. 6924 (f)(2)). This schedule reguires that EPA develop land disposal restrictions for deep well injection by August 8, 1988. The amendments also require the Agency to set "levels or v methods of treatment, if any, which substantially diminish the toxicity of the waste or substantially reduce the likelihood of migration of hazardous constituents from the waste so that 1-2 Rev. 3 ------- short-term and long-term threats to human health and the environment are minimized" (RCRA section 3004(m)(l), 42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established by EPA are not prohibited and may be land disposed. In setting treatment standards for listed or characteristic wastes, EPA may establish different standards for particular wastes within a single waste code with differing treatability characteristics. One such characteristic is the physical form of the waste. This frequently leads to different standards for wastewaters and nonwastewaters. Alternatively, EPA can establish a treatment standard that is applicable to more than one waste code when, in EPA's judgment, all the waste can be treated to the same concentration. In those instances where a generator can demonstrate that the standard promulgated for the generator's waste cannot be achieved, the Agency also can grant a variance from a treatment standard by revising the treatment standard for that particular waste through rulemaking procedures. (A further discussion of treatment variances is provided in Section 1.3.) The land disposal restrictions are effective when promulgated unless the Administrator grants a national variance V and establishes a different date (not to exceed 2 years beyond the statutory deadline) based on "the earliest date on which adequate alternative treatment, recovery, or disposal capacity 1-3 Rev. 3 ------- which protects human health and the environment will be available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)). If EPA fails to set a treatment standard by the statutory deadline for any hazardous waste in the First Third or Second Third of the schedule (see section 1.1.2), the waste may not be disposed in a landfill or surface impoundment unless the facility is in compliance with the minimum technological requirements specified in section 3004(o) of RCRA. In addition, prior to disposal, the generator must certify to the Administrator that the availability of treatment capacity has been investigated and it has been determined that disposal in a landfill or surface impoundment is the only practical alternative to treatment currently available to the generator. This restriction on the use of landfills and surface impoundments applies until EPA sets a treatment standard for the waste or until May 8, 1990, whichever is sooner. If the Agency fails to set a treatment standard for any ranked hazardous waste by May 8, 1990, the waste is automatically prohibited from land disposal unless the waste is placed in a land disposal unit that is the subject of a successful "no migration" demonstration (RCRA section 3004(g), 42 U.S.C. 6924(g)). "No migration" demonstrations are based on case-specific petitions that show there will be no migration of hazardous constituents from the unit for as long as the waste remains hazardous. 1-4 Rev. 3 ------- 1.1.2 Schedule for Developing Restrictions Under Section 3004(g) of RCRA, EPA was required to e»tablish a schedule for developing treatment standards for all wastes that the Agency had listed as hazardous by November 8, 1984. Section 3004(g) required that this schedule consider the intrinsic hazards and volumes associated with each of these wastes. The statute required EPA to set treatment standards according to the following schedule: (a) Solvents and dioxins standards must be promulgated by November 8, 1986; (b) The "California List" must be promulgated by July 8, 1987; (c) At least one-third of all listed hazardous wastes must be promulgated by August 8, 1988 (First Third); (d) At least two-thirds of all listed hazardous wastes must be promulgated by June 8, 1989 (Second Third); and (e) All remaining listed hazardous wastes and all hazardous wastes identified as of November 8, 1984, by one or more of the characteristics defined in 40 CFR Part 261 must be promulgated by May 8, 1990 (Third Third). The statute specifically identified the solvent wastes as those covered under waste codes F001, F002, F003, F004, and F005; it identified the dioxin-containing hazardous wastes as those covered under waste codes F020, F021, F022, and F023. Wastes collectively known as the California List wastes, defined under Section 3004(d) of HSWA, are liquid hazardous wastes containing metals, free cyanides, PCBs, corrosives (i.e., 1-5 Rev. 3 ------- a pH less than or equal to 2.0), and any liquid or nonliquid hazardous waste containing halogenated organic compounds (HOCs) above 0.1 percent by weight. Rules for the California List were proposed on December 11, 1986, and final rules for PCBs, corrosives, and HOC-containing wastes were established August 12, 1987. In that rule, EPA elected not to establish standards for metals. Therefore, the statutory limits became effective. On May 28, 1986, EPA published a final rule (51 FR 19300) that delineated the specific waste codes that would be addressed by the First Third, Second Third, and Third Third. This schedule is incorporated into 40 CFR 268.10, .11, and .12. 1.2 Summary of Promulgated BOAT Methodology In a November 7, 1986, rulemaking, EPA promulgated a technology-based approach to establishing treatment standards under section 3004(m). Section 3004(m) also specifies that treatment standards must "minimize" long- and short-term threats to human health and the environment arising from land disposal of hazardous wastes. v- Congress indicated in the legislative history accompanying the HSWA that "[t]he requisite levels of [sic] methods of treatment established by the Agency should be the best that has 1-6 Rev. 3 ------- been demonstrated to be achievable," noting that the intent is "to require utilization of available technology" and not a "process which contemplates technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed., July 25, 1984)). EPA has interpreted this legislative history as suggesting that Congress considered the requirement under 3004(m) to be met by application of the best demonstrated and achievable (i.e., available) technology prior to land disposal of wastes or treatment residuals. Accordingly, EPA's treatment standards are generally based on the performance of the best demonstrated available technology (BOAT) identified for treatment of the hazardous constituents. This approach involves the identification of potential treatment systems, the determination of whether they are demonstrated and available, and the collection of treatment data from well-designed and well-operated systems. The treatment standards, according to the statute, can represent levels or methods of treatment, if any, that substantially diminish the toxicity of the waste or substantially reduce the likelihood of migration of hazardous constituents. Wherever possible, the Agency prefers to establish BOAT treatment standards as "levels" of treatment (i.e., performance standards) rather than adopting an approach that would require the use of specific treatment "methods." EPA believes that concentration-based treatment levels offer the regulated community greater flexibility to develop and implement compliance 1-7 Rev. 3 ------- strategies as well as an incentive to develop innovative technologies. 1.2.1 Waste Treatability Group In developing the treatment standards, EPA first characterizes the waste(s). As necessary, EPA may establish treatability groups for wastes having similar physical and chemical properties. That is, if EPA believes that wastes represented by different waste codes could be treated to similar concentrations using identical technologies, the Agency combines the codes into one treatability group. EPA generally considers wastes to be similar when they are both generated from the same industry and from similar processing stages. In addition, EPA may combine two or more separate wastes into the same treatability group when data are available showing that the waste characteristics affecting performance are similar or that one waste would be expected to be less difficult to treat. Once the treatability groups have been established, EPA collects and analyzes data on identified technologies used to treat the wastes in each treatability group. The technologies evaluated must be demonstrated on the waste or a similar waste and must be available for use. 1-8 Rev. 3 ------- 1.2.2 Demonstrated and Available Treatment Technologies Consistent with legislative history, EPA considers demonstrated technologies to be those that are used to treat the waste of interest or a similar waste with regard to parameters that affect treatment selection (see November 7, 1986, 51 FR 40588). EPA also will consider as treatment those technologies used to separate or otherwise process chemicals and other materials. Some of these technologies clearly are applicable to waste treatment, since the wastes are similar to raw materials processed in industrial applications. For most of the waste treatability groups for which EPA will promulgate treatment standards, EPA will identify demonstrated technologies either through review of literature related to current waste treatment practices or on the basis of information provided by specific facilities currently treating the waste or similar wastes. In cases where the Agency does not identify any facilities treating wastes represented by a particular waste treatability group, EPA may transfer a finding of demonstrated treatment. To do this, EPA will compare the parameters affecting treatment •r selection for the waste treatability group of interest to other wastes for which demonstrated technologies already have been determined. The parameters affecting treatment selection and 1-9 Rev. 3 ------- their use for this waste are described in Section 3.2 of this document. If the parameters affecting treatment selection are similar, then the Agency will consider the treatment technology also to be demonstrated for the waste of interest. For example, EPA considers rotary kiln incineration a demonstrated technology for many waste codes containing hazardous organic constituents, high total organic content, and high filterable solids content, regardless of whether any facility is currently treating these wastes. The basis for this determination is data found in literature and data generated by EPA confirming the use of rotary kiln incineration on wastes having the above characteristics. If no commercial treatment or recovery operations are identified for a waste or wastes with similar physical or chemical characteristics that affect treatment selection, the Agency will be unable to identify any demonstrated treatment technologies for the waste, and, accordingly, the waste will be prohibited from land disposal (unless handled in accordance with the exemption and variance provisions of the rule). The Agency is, however, committed to establishing treatment standards as soon as new or improved treatment processes are demonstrated (and available). V Operations only available at research facilities, pilot- and bench- scale operations will not be considered in identifying demonstrated treatment technologies for a waste because these 1-10 Rev. 3 ------- technologies would not necessarily be "demonstrated." Nevertheless, EPA may use data generated at research facilities in assessing the performance of demonstrated technologies. As discussed earlier, Congress intended that technologies used to establish treatment standards under Section 3004(m) be not only "demonstrated," but also available. To decide whether demonstrated technologies may be considered "available," the Agency determines whether they (1) are commercially available and (2) substantially diminish the toxicity of the waste or substantially reduce the likelihood of migration of hazardous constituents from the waste. EPA will only set treatment standards based on a technology that meets the above criteria. Thus, the decision to classify a technology as "unavailable" will have a direct impact on the treatment standard. If the best technology is unavailable, the treatment standard will be based on the next best treatment technology determined to be available. To the extent that the resulting treatment standards are less stringent, greater concentrations of hazardous constituents in the treatment residuals could be placed in land disposal units. There also may be circumstances in which EPA concludes that for a given waste none of the demonstrated treatment technologies are "available" for purposes of establishing the 3004(m) 1-11 Rev. 3 ------- treatment performance standards. Subsequently, these wastes will be prohibited from continued placement in or on the land unless managed in accordance with applicable exemptions and variance provisions. The Agency is, however, committed to establishing new treatment standards as soon as new or improved treatment processes become "available." (1) Proprietary or Patented Processes. If the demonstrated treatment technology is a proprietary or patented process that is not generally available, EPA will not consider the technology in its determination of the treatment standards. EPA will consider proprietary or patented processes available if it determines that the treatment method can be purchased or licensed from the proprietor or is commercially available treatment. The services of the commercial facility offering this technology often can be purchased even if the technology itself cannot be purchased. (2) Substantial Treatment. To be considered "available," a demonstrated treatment technology must "substantially diminish the toxicity" of the waste or "substantially reduce the likelihood of migration of hazardous constituents" from the waste in accordance with section 3004(m). By requiring that substantial treatment be achieved in order to set a treatment V standard, the statute ensures that all wastes are adequately treated before being placed in or on the land and ensures that the Agency does not require a treatment method that provides 1-12 Rev. 3 ------- little or no environmental benefit. Treatment will always be deemed substantial if it results in nondetectable levels of the hazardous constituents of concern. If nondetectable levels are not achieved, then a determination of substantial treatment will be made on a case-by-case basis. This approach is necessary because of the difficulty of establishing a meaningful guideline that can be applied broadly to the many wastes and technologies to be considered. EPA will consider the following factors in an effort to evaluate whether a technology provides substantial treatment on a case-by-case basis: (a) Number and types of constituents treated; (b) Performance (concentration of the constituents in the treatment residuals); and (c) Percent of constituents removed. If none of the demonstrated treatment technologies achieve substantial treatment of a waste, the Agency cannot establish treatment standards for the constituents of concern in that waste. 1.2.3 Collection of Performance Data Performance data on the demonstrated available technologies • are evaluated by the Agency to determine whether the data are representative of well-designed and well-operated treatment systems. Only data from well-designed and well-operated systems 1-13 Rev. 3 ------- are included in determining BOAT. The data evaluation includes data already collected directly by EPA and/or data provided by industry. In those instances where additional data are needed to supplement existing information, EPA collects additional data through a sampling and analysis program. The principal elements of this data collection program are: (a) identification of facilities for site visits, (b) engineering site visit, (c) Sampling and Analysis Plan, (d) sampling visit, and (e) Onsite Engineering Report. (1) Identification of Facilities for Site Visits. To identify facilities that generate and/or treat the waste of concern, EPA uses a number of information sources. These include Stanford Research Institute's Directory of Chemical Producers, EPA's Hazardous Waste Data Management System (HWDMS), the 1986 Treatment, Storage, Disposal Facility (TSDF) National Screening Survey, and EPA's Industry Studies Data Base. In addition, EPA contacts trade associations to inform them that the Agency is considering visits to facilities in their industry and to solicit assistance in identifying facilities for EPA to consider in its treatment sampling program. After identifying facilities that treat the waste, EPA uses v this hierarchy to select sites for engineering visits: (1) generators treating single wastes on site; (2) generators treating multiple wastes together on site; (3) commercial 1-14 Rev. 3 ------- treatment, storage, and disposal facilities (TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two concepts: (1) to the extent possible, EPA should develop treatment standards from data produced by treatment facilities handling only a single waste, and (2) facilities that routinely treat a specific waste have had the best opportunity to optimize design parameters. Although excellent treatment can occur at many facilities that are not high in this hierarchy, EPA has adopted this approach to avoid, when possible, ambiguities related to the mixing of wastes before and during treatment. When possible, the Agency will evaluate treatment technologies using commercially operated systems. If performance data from properly designed and operated commercial treatment methods for a particular waste or a waste judged to be similar are not available, EPA may use data from research facilities operations. Whenever research facility data are used, EPA will explain why such data were used in the preamble and background document and will request comments on the use of such data. Although EPA's data bases provide information on treatment for individual wastes, the data bases rarely provide data that support the selection of one facility for sampling over another. In cases where several treatment sites appear to fall into the same level of the hierarchy, EPA selects sites for visits strictly on the basis of which facility could most expeditiously 1-15 Rev. 3 ------- be visited and later sampled if justified by the engineering visit. (2) Engineering Site Visit. Once a treatment facility has been selected, an engineering site visit is made to confirm that a candidate for sampling meets EPA's criteria for a well-designed facility and to ensure that the necessary sampling points can be accessed to determine operating parameters and treatment effectiveness. During the visit, EPA also confirms that the facility appears to be well operated, although the actual operation of the treatment system during sampling is the basis for EPA's decisions regarding proper operation of the treatment unit. In general, the Agency considers a well-designed facility to be one that contains the unit operations necessary to treat the various hazardous constituents of the waste as well as to control other nonhazardous materials in the waste that may affect treatment performance. In addition to ensuring that a system is reasonably well designed, the engineering visit examines whether the facility has a way to measure the operating parameters that affect performance of the treatment system during the waste treatment period. For example, EPA may choose not to sample a treatment system that operates in a continuous mode, for which an important operating parameter cannot be continuously recorded. In such systems, instrumentation is important in determining whether the treatment 1-16 Rev. 3 ------- system is operating at design values during the waste treatment period. (3) Sampling and Analysis Plan. If after the engineering site visit the Agency decides to sample a particular plant, the Agency will then develop a site-specific Sampling and Analysis Plan (SAP) according to the Generic Quality Assurance Project Plan for the Land Disposal Restriction Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where the Agency plans to sample, how the samples will be taken, the frequency of sampling, the constituents to be analyzed and the method of analysis, operational parameters to be obtained, and specific laboratory quality control checks on the analytical results. The Agency will generally produce a draft of the site-specific Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit. The draft of the SAP is then sent to the plant for review and comment. With few exceptions, the draft SAP should be a confirmation of data collection activities discussed with the plant personnel during the engineering site visit. EPA encourages plant personnel to recommend any modifications to the SAP that they believe will improve the quality of the data. It is important to note that sampling of a plant by EPA does not mean that the data will be used in the development of treatment standards for BOAT. EPA's final decision on whether to 1-17 Rev. 3 ------- use data from a sampled plant depends on the actual analysis of the waste being treated and on the operating conditions at the time of sampling. Although EPA would not plan to sample a facility that was not ostensibly well-designed and well-operated, there is no way to ensure that at the time of the sampling the facility will not experience operating problems. Additionally, EPA statistically compares its test data to suitable industry-provided data, where available, in its determination of what data to use in developing treatment standards. The methodology for comparing data is presented later in this section. (Note: Facilities wishing to submit data for consideration in the development of BOAT standards should, to the extent possible, provide sampling information similar to that acquired by EPA. Such facilities should review the Generic Quality Assurance Project Plan for the Land Disposal Restriction Program ("BOAT"), which delineates all of the quality control and quality assurance measures associated with sampling and analysis. Quality assurance and quality control procedures are summarized in Section 1.2.6 of this document.) (4) Sampling Visit. The purpose of the sampling visit is v to collect samples that characterize the performance of the treatment system and to document the operating conditions that existed during the waste treatment period. At a minimum, the 1-18 Rev. 3 ------- Agency attempts to collect sufficient samples of the untreated waste and solid and liquid treatment residuals so that variability in the treatment process can be accounted for in the development of the treatment standards. To the extent practicable, and within safety constraints, EPA or its contractors collect all samples and ensure that chain-of-custody procedures are conducted so that the integrity of the data is maintained. In general, the samples collected during the sampling visit will have already been specified in the SAP. In some instances, however, EPA will not be able to collect all planned samples because of changes in the facility operation or plant upsets; EPA will explain any such deviations from the SAP in its follow-up Onsite Engineering Report. (5) Onsite Engineering Report. EPA summarizes all its data collection activities and associated analytical results for testing at a facility in a report referred to as the Onsite Engineering Report (OER). This report characterizes the waste(s) treated, the treated residual concentrations, the design and operating data, and all analytical results including methods used and accuracy results. This report also describes any deviations • from EPA's suggested analytical methods for hazardous wastes (Test Methods for Evaluating Solid Waste, SW-846, Third Edition, November 1986). 1-19 Rev. 3 ------- After the Onsite Engineering Report is completed, the report is submitted to the plant for review. This review provides the plant with a final opportunity to claim any information contained in the report as confidential. Following the review and incorporation of comments, as appropriate, the report is made available to the public with the exception of any material claimed as confidential by the plant. 1.2.4 Hazardous Constituents Considered and Selected for Regulation (1) Development of BOAT List. The list of hazardous constituents within the waste codes that are targeted for treatment is referred to by the Agency as the BDAT constituent list. This list, provided as Table 1-1, is derived from the constituents presented in 40 CFR Part 261, Appendix VII and Appendix VIII, as well as several ignitable constituents used as the basis of listing wastes as F003 and F005. These sources provide a comprehensive list of hazardous constituents specifically regulated under RCRA. The BDAT list consists of those constituents that can be analyzed using methods published in SW-846, Third Edition. The initial BDAT constituent list was published in EPA's Generic Quality Assurance Project Plan, March 1987 (EPA/530-SW-87-011). Additional constituents will be added to 1-20 Rev. 3 ------- 1521g Table 1-1 BOAT Constituent List BOAT reference no. 222. 1. 2. 3. 4. 5. 6. 223. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25 26. 27. 28. 29. 224. 225. 226. 30. 227. 31. 214. 32 Parameter Volatiles Acetone Acetomtn le Acrolein Acrylomtnle Benzene Bromodichloromethane Bromomethane n-Butyl alcohol Carbon tetrachloride Carbon disulfide Chlorobenzene 2-Chloro-l ,3-butadiene Chlorodibromomethane Chloroethane 2-Chloroethyl vinyl ether Chloroform Chloromethane 3-Chloropropene 1 , 2-Dibromo-3-chloropropane 1 ,2-Dibromoethane Dibromomethane Trans -1 ,4-Dichloro-2-butene Dichlorodif luorome thane 1, 1-Oichloroethane 1,2-Oichloroethane 1,1-Dichloroethylene Trans-1 , 2-Dichloroethene 1,2-Oichloropropane Trans-1 ,3-Oichloropropene cis-1 ,3-Dichloropropene 1 ,4-Dioxane 2-Ethoxyethanol Ethyl acetate Ethyl benzene Ethyl cyan'de Ethyl ether Ethyl methacrylate Ethylene oxide lodomethane Cas no. 67-64-1 75-05-8 107-02-8 107-13-1 71-43-2 75-27-4 74-83-9 71-36-3 56-23-5 75-15-0 108-90-7 126-99-8 124-48-1 75-00-3 110-75-8 67-66-3 74-87-3 107-05-1 96-12-8 106-93-4 74-95-3 110-57-6 75-71-8 75-34-3 107-06-2 75-35-4 156-60-5 78-87-5 10061-02-6 10061-01-5 123-91-1 60-29-7 141-78-6 100-41-4 107-12-0 60-29-7 97-63-2 75-21-8 74-88-4 1-21 Rev. 3 ------- 1521g Table 1-1 (continued) BOAT reference no. 33. 228. 34. 229. 35. 37. 38. 230. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 231. 50. 215. 216. 217. 51. 52. 53. 54. 55. 56. 57. 58. 59. 218. 60. 61. 62. Parameter Volatiles (continued) Isobutyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone Methyl methacrylate Methacrylonitri le Methylene chloride 2-Nitropropane Pyridine 1,1, 1,2-Tetrachloroethane 1,1,2, 2-Tet rach loroethane Tetrachloroethene Toluene Tribromomethane 1,1, 1-Trichloroethane 1,1, 2-Trichloroethane Tnchloroethene Tr i ch loromonof luoromethane 1,2,3-Trichloropropane l,l,2-Trichloro-l,2,2-tnf luoro- ethane Vinyl chloride 1,2-Xylene 1,3-Xylene 1,4-Xylene Sennvolat i les Acenaphthalene Acenaphthene Acetophenone 2-Acetylaminof luorene 4-Aminobiphenyl Aniline Anthracene Aramite Benz(a)anthracene Benzal chloride Benzenethiol Deleted Benzo(a)pyrene Cas no. 78-83-1 67-56-1 78-93-3 108-10-1 80-62-6 126-98-7 75-09-2 79-46-9 110-86-1 630-20-6 79-34-6 127-18-4 108-88-3 75-25-2 71-55-6 79-00-5 79-01-6 75-69-4 96-18-4 76-13-1 75-01-4 97-47-6 108-38-3 106-44-5 208-96-8 83-32-9 96-86-2 53-96-3 92-67-1 62-53-3 120-12-7 140-57-8 56-55-3 98-87-3 108-98-5 50-32-8 1-22 Rev. 3 ------- 1521g Table 1-1 (continued) BOAT reference no. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 232. 83. 84. 85. 86.' 87. 88. 89. 90. 91. 92. 93. 94. 95 96. 97. 98. 99 100. 101. Parameter Semivolatiles (continued) Benzo(b)f luoranthene Benzo(ghi )pery lene Benzo(k)f luoranthene p-Benzoquinone Bis(2-chloroethoxy)methane Bis(2-chloroethyl)ether Bis(2-chloroisopropyl)ether Bis(2-ethylhexyl)phthalate 4-Bromophenyl phenyl ether Butyl benzyl phthalate 2-sec-Butyl-4,6-dinitrophenol p-Chloroani line Chlorobenzi late p-Chloro-m-cresol 2-Chloronaphthalene 2-Chlorophenol 3-Chloropropionitri le Chrysene ortho-Cresol para-Cresol Cyclohexanone 0 i benz( a, h) anthracene Dibenzo(a,e)pyrene Oibenzo(a, i)pyrene m-Oichlorobenzene o-Dichlorobenzene p-Oichlorobenzene 3,3'-Oichlorobenzidine 2,4-Oichlorophenol 2,6-Oichlorophenol Diethyl phthalate 3,3'-Dimethoxybenzidine p-D imethy lami noazobenzene 3,3'-Oimethylbenzidine 2,4-Dimethylphenol Dimethyl phthalate Di-n-butyl phthalate 1 ,4-Oinitrobenzene 4,6-Dinitro-o-cresol 2,4-Dinitrophenol CAS no. 205-99-2 191-24-2 207-08-9 106-51-4 111-91-1 111-44-4 39638-32-9 117-81-7 101-55-3 85-68-7 88-85-7 106-47-8 510-15-6 59-50-7 91-58-7 95-57-8 542-76-7 218-01-9 95-48-7 106-44-5 108-94-1 53-70-3 192-65-4 189-55-9 541-73-1 95-50-1 106-46-7 91-94-1 120-83-2 87-65-0 84-66-2 119-90-4 60-11-7 119-93-7 105-67-9 131-ll-3 84-74-2 100-25-4 534-52-1 51-28-5 1-23 Rev. 3 ------- ISZlg Table 1-1 (continued) BOAT reference no. 102. 103. 104. 105. 106. 219. 107. 108. 109. 110. 111. 112. 113. 114. 115. 116. 117. 118. 119. 120. 36. 121. 122. 123. 124. 125. 126. 127. 128. 129. 130. 131. 132. 133. 134. 135. 136. 137. 138. Parameter Semivolatlles (continued) 2,4-Dinitrotoluene 2,6-Oinitrotoluene Di-n-octyl phthalate Di-n-propylnitrosannne Diphenylamine D 1 pheny 1 n i t rosam i ne 1 , 2-D ipheny Ihydraz i ne Fluoranthene Fluorene Hexach lorobenzene Hexachlorobutadiene Hexachlorocyclopentadiene Hexach loroethane Hexach lorophene Hexach loropropene Indeno(l,2,3-cd)pyrene Isosafrole Methapyri lene 3-Met hy 1cho lanthrene 4,4'-Methylenebis (2-chloroamline) Methyl methanesulfonate Naphthalene 1 ,4-Naphthoquinone 1-Naphthylamine 2-Naphthylamine p-Nitroani line Nitrobenzene 4-Nitrophenol N-Nitrosodi-n-butylamine N-Nitrosodiethylamine N-Nitrosodimethylamine N-Nitrosomethylethylamine N-Nitrosomorpholine N-Nitrosopipendine n-Nitrosopyrrolidine 5-Nitro-o-toluidine Pentachlorobenzene Pentach loroethane Pentach loron i t robenzene CAS no. 121-14-2 606-20-2 117-84-0 621-64-7 122-39-4 86-30-6 122-66-7 206-44-0 86-73-7 118-74-1 87-68-3 77-47-4 67-72-1 70-30-4 1888-71-7 193-39-5 120-58-1 - 91-80-5 56-49-5 101-14-4 66-27-3 91-20-3 130-15-4 134-32-7 91-59-8 100-01-6 98-95-3 100-02-7 924-16-3 55-18-5 62-75-9 10595-95-6 59-89-2 100-75-4 930-55-7 99-65-8 608-93-5 76-01-7 82-68-8 1-24 Rev. 3 ------- 1521g Table 1-1 (continued) BOAT reference no. 139. 140. 141. 142. 220. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 221. 160. 161. 162. 163. 164. 165. 166. 167. 168. 169. 170. 171. Parameter Semivolatiles (continued) Pentachlorophenol Phenacetin Phenanthrene Phenol Phthalic anhydride 2-Picoline Pronamide Pyrene Resorcinol Safrole 1 , 2 , 4 , 5-Tetrach lorobenzene 2,3,4, 6-Tet rach loropheno 1 1 . 2 , 4-Tr i en lorobenzene 2, 4, 5-Tnch loropheno 1 2, 4, 6-Tricn loropheno 1 Tris(2,3-dibromopropyl) phosphate Metals Antimony Arsenic Barium Beryl lium Cadmium Chromium (total) Chromium (hexavalent) Copper Lead Mercury Nickel Selenium Si Iver Tha 1 1 i urn Vanadium Zinc Inorganics Cyanide Fluoride Sulfide CAS no. 87-86-5 62-44-2 85-01-8 108-95-2 85-44-9 109-06-8 23950-58-5 129-00-0 108-46-3 94-59-7 95-94-3 58-90-2 120-82-1 95-95-4 88-06-2 126-72-7 7440-36-0 7440-38-2 7440-39-3 7440-41-7 7440-43-9 7440-47-32 - 7440-50-8 7439-92-1 7439-97-6 7440-02-0 7782-49-2 7440-22-4 7440-28-0 7440-62-2 7440-6&-6 57-12-5 16964-48-8 8496-25-8 1-25 Rev. 3 ------- 1521g Table 1-1 (continued) BOAT reference no. 172. 173. 174. 175. 176. 177. 178. 179. 180. 181. 182. 183. 184. 185. 186. 187. 188. 189. 190. 191. 192. 193. 194. 195. 196. 197. 198. 199. 200. 201. 202. Parameter Orqanochlorine pesticides Aldrin alpha-BHC beta-BHC delta-BHC ganma-BHC Chlordane ODD DOE DDT Dieldrin Endosulfan I Endosulfan II Endrin Endrin aldehyde Heptachlor Heptachlor epoxide Isodrin tCepone Methoxyclor Toxaphene Phenoxvacet ic acid herbicides 2,4-Dichlorophenoxyacetic acid Si Ivex 2.4,5-T Orqanoohosphorous insecticides Disulfoton Fampnur Methyl parathion Parathion Phorate PCBs Aroclor 1016 Aroclor 1221 Aroclor 1232 CAS no. 309-00-2 319-84-6 319-85-7 319-86-8 58-89-9 57-74-9 72-54-8 72-55-9 50-29-3 60-57-1 939-98-8 33213-6-5 72-20-8 7421-93-4 76-44-8 1024-57-3 465-73-6 143-50-0 72-43-5 8001-35-2 94-75-7 93-72-1 93-76-5 298-04-4 52-85-7 298-00-0 56-38-2 298-02-2 V 12674-11-2 11104-28-2 11141-16-5 1-26 Rev. 3 ------- 1521g Table 1-1 (continued) BOAT reference Parameter CAS no. PCBs (continued) 203. Aroclor 1242 53469-21-9 204. Aroclor 1248 12672-29-6 205. Aroclor 1254 11097-69-1 206. Aroclor 1260 11096-82-5 Oioxins and furans 207. Hexachlorodibenzo-p-dioxins 208. Hexachlorodibenzofurans 209. Pentachlorodibenzo-p-dioxins 210. Pentachlorodibenzofurans 211. Tetrachlorodibenzo-p-dioxins 212. Tetrachlorodibenzofurans 213. 2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6 1-27 Rev. 3 ------- the BOAT constituent list as additional key constituents are identified for specific waste codes or as new analytical methods are developed for hazardous constituents. For example, since the list was published in March 1987, eighteen additional constituents (hexavalent chromium, xylene (all three isomers), benzal chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol, 2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol, methyl isobutyl ketone, 2-nitropropane, l,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have been added to the list. Chemicals are listed in Appendix VIII if they are shown in scientific studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on humans or other life-forms, and they include such substances as those identified by the Agency's Carcinogen Assessment Group as being carcinogenic. Including a constituent in Appendix VIII means that the constituent can be cited as a basis for listing toxic wastes. Although Appendix VII, Appendix VIII, and the F003 and F005 ignitables provide a comprehensive list of RCRA-regulated hazardous constituents, not all of the constituents can be analyzed in a complex waste matrix. Therefore, constituents that could not be readily analyzed in an unknown waste matrix were not included on the initial BOAT list. As mentioned above, however, the BDAT constituent list is a continuously growing list that 1-28 Rev. 3 ------- does not preclude the addition of new constituents when analytical methods are developed. There are 5 major reasons that constituents were not included on the BOAT constituent list: (a) Constituents are unstable. Based on their chemical structure, some constituents will either decompose in water or will ionize. For example, maleic anhydride will form maleic acid when it comes in contact with water and copper cyanide will ionize to form copper and cyanide ions. However, EPA may choose to regulate the decomposition or ionization products. (b) EPA-approved or verified analytical methods are not available. Many constituents, such as 1,3,5-trinitrobenzene, are not measured adequately or even detected using any of EPA's analytical methods published in SW-846 Third Edition. (c) The constituent is a member of a chemical group designated in Appendix VIII as not otherwise specified (N.O.S.). Constituents listed as N.O.S., such as chlorinated phenols, are a generic group of some types of chemicals for which a single analytical procedure is not available. The individual members of each such group need to be listed to determine whether the constituents can be analyzed. For each N.O.S. group, all those constituents that can be readily analyzed are included in the BDAT constituents list. (d) Available analytical procedures are not appropriate for a complex waste matrix. Some compounds, such as auramine, can be analyzed as a pure constituent. However, in the presence of other constituents, the recommended analytical method does not positively identify the constituent. The use of high pressure liquid chromotography (HPLC) presupposes a high expectation of finding the specific constituents of interest. In using this procedure to screen samples, protocols would have to be developed on a case-specific basis to verify the identity of constituents present in the samples. Therefore, HPLC is not an appropriate analytical procedure for complex samples containing 1-29 Rev. 3 ------- unkown constituents. (e) Standards for analytical instrument calibration are not commercially available. For several constituents, such as benz(c)acridine, commercially available standards of a "reasonably" pure grade are not available. The unavailability of a standard was determined by a review of catalogs from specialty chemical manufacturers. Two constituents (fluoride and sulfide) are not specifically included in Appendices VII and VIII; however, these compounds are included on the BOAT list as indicator constituents for compounds from Appendices VII and VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in water. The BOAT constituent list presented in Table 1-1 is divided into the following nine groups: o Volatile organics o Semivolatile organics o Metals o Other inorganics o Organochlorine pesticides o Phenoxyacetic acid herbicides o Organophosphorous insecticides o PCBs o Dioxins and furans The constituents were placed in these categories based on their chemical properties. The constituents in each group are expected to behave similarily during treatment and are also analyzed, with the exception of the metals and inorganics, by using the same y analytical methods. 1-30 Rev. 3 ------- (2) Constituent Selection Analysis. The constituents that the Agency selects for regulation in each treatability group are, in general, those found in the untreated wastes at treatable concentrations. For certain waste codes, the target list for the untreated waste may have been shortened (relative to analyses performed to test treatment technologies) because of the extreme unlikelihood of the constituent being present. In selecting constituents for regulation, the first step is to summarize all the constituents that were found in the untreated waste at treatable concentrations. This process involves the use of the statistical analysis of variance (ANOVA) test, described in Section 1.2.6, to determine if constituent reductions were significant. The Agency interprets a significant reduction in concentration as evidence that the technology actually "treats" the waste. There are some instances where EPA may regulate constituents that are not found in the untreated waste but are detected in the treated residual. This is generally the case where presence of the constituents in the untreated waste interferes with the quantification of the constituent of concern. In such instances, the detection levels of the constituent are relatively high, resulting in a finding of "not detected" when, in fact, the constituent is present in the waste. 1-31 Rev. 3 ------- After determining which of the constituents in the untreated waste are present at treatable concentrations, EPA develops a list of potential constituents for regulation. The Agency then reviews this list to determine if any of these constituents can be excluded from regulation because they would be controlled by regulation of other constituents in the list. EPA performs this indicator analysis for two reasons: (1) it reduces the analytical cost burdens on the treater and (2) it facilitates implementation of the compliance and enforcement program. EPA's rationale for selection of regulated constituents for this waste code is presented in Section 5 of this background document. (3) Calculation of Standards. The final step in the calculation of the BDAT treatment standard is the multiplication of the average treatment value by a factor referred to by the Agency as the variability factor. This calculation takes into account that even well-designed and well-operated treatment systems will experience some fluctuations in performance. EPA expects that fluctuations will result from inherent mechanical limitations in treatment control systems, collection of treated samples, and analysis of these samples. All of the above V fluctuations can be expected to occur at well-designed and well-operated treatment facilities. Therefore, setting treatment standards utilizing a variability factor should be viewed not as 1-32 Rev. 3 ------- a relaxing of 3004(m) requirements, but rather as a function of the normal variability of the treatment processes. A treatment facility will have to be designed to meet the mean achievable treatment performance level to ensure that the performance levels remain within the limits of the treatment standard. The Agency calculates a variability factor for each constituent of concern within a waste treatability group using the statistical calculation presented in Appendix A. The equation for calculating the variability factor is the same as that used by EPA for the development of numerous regulations in the Effluent Guidelines Program under the Clean Water Act. The variability factor establishes the instantaneous maximum based on the 99th percentile value. There is an additional step in the calculation of the treatment standards in those instances where the ANOVA analysis shows that more than one technology achieves a level of performance that represents BOAT. In such instances, the BOAT treatment standard is calculated by first averaging the mean performance value for each technology for each constituent of concern and then multiplying that value by the highest variability factor among the technologies considered. This procedure ensures that all the BOAT technologies used as the basis for the standards will achieve full compliance. 1-33 Rev. 3 ------- 1.2.5 Compliance with Performance Standards All the treatment standards reflect performance achieved by the Best Demonstrated Available Technology (BOAT). As such, compliance with these standards only requires that the treatment level be achieved prior to land disposal. It does not require the use of any particular treatment technology. While dilution of the waste as a means to comply with the standard is prohibited, wastes that are generated in such a way as to naturally meet the standard can be land disposed without treatment. With the exception of treatment standards that prohibit land disposal, all treatment standards proposed are expressed as a concentration level. EPA has used both total constituent concentration and TCLP analyses of the treated waste as a measure of technology performance. EPA's rationale for when each of these analytical tests is used is explained in the following discussion. For all organic constituents, EPA is basing the treatment standards on the total constituent concentration found in the treated waste. EPA based its decision on the fact that technologies exist to destroy the various organics compounds. V Accordingly, the best measure of performance would be the extent to which the various organic compounds have been destroyed or the total amount of constituent remaining after treatment. (NOTE: 1-34 Rev. 3 ------- EPA's land disposal restrictions for solvent waste codes F001-F005 (51 FR 40572) uses the TCLP value as a measure of performance. At the time that EPA promulgated the treatment standards for F001-F005, useful data were not available on total constituent concentrations in treated residuals and, as a result, the TCLP data were considered to be the best measure of performance.) For all metal constituents, EPA is using both total constituent concentration and/or the TCLP as the basis for treatment standards. The total constituent concentration is being used when the technology basis includes a metal recovery operation. The underlying principle of metal recovery is the reduction of the amount of metal in a waste by separating the metal for recovery; therefore, total constituent concentration in the treated residual is an important measure of performance for this technology. Additionally, EPA also believes that it is important that any remaining metal in a treated residual waste not be in a state that is easily leachable; accordingly, EPA is also using the TCLP as a measure of performance. It is important to note that for wastes for which treatment standards are based on a metal recovery process, the facility has to comply with both the total constituent concentration and the TCLP prior to land • disposal. 1-35 Rev. 3 ------- In cases where treatment standards for metals are not based on recovery techniques but rather on stabilization, EPA is using only the TCLP as a measure of performance. The Agency's rationale is that stabilization is not meant to reduce the concentration of metal in a waste but only to chemically minimize the ability of the metal to leach. 1.2.6 Identification of BOAT (1) Screening of Treatment Data. This section explains how the Agency determines which of the treatment technologies represent treatment by BOAT. The first activity is to screen the treatment performance data from each of the demonstrated and available technologies according to the following criteria: (a) Design and operating data associated with the treatment data must reflect a well-designed, well-operated system for each treatment data point. (The specific design and operating parameters for each demonstrated technology for this waste code are discussed in Section 3.2 of this document.) (b) Sufficient QA/QC data must be available to determine the true values of the data from the treated waste. This screening criterion involves adjustment of treated data to take into account that the type value may be different from the measured value. This discrepancy generally is caused by other constituents in the waste that can mask results or otherwise interfere with the analysis of the constituent of concern. (c) The measure of performance must be consistent with EPA's approach to evaluating treatment by type of constituents (e.g., total concentration data for organics, and total concentration and TCLP for metals in the leachate from the residual). 1-36 Rev. 3 ------- In the absence of data needed to perform the screening analysis, EPA will make decisions on a case-by-case basis of whether to include the data. The factors included in this case-by-case analysis will be the actual treatment levels achieved, the availability of the treatment data and their completeness (with respect to the above criteria), and EPA's assessment of whether the untreated waste represents the waste code of concern. EPA's application of these screening criteria for this waste code are provided in Section 4 of this background document. (2) Comparison of Treatment Data. In cases in which EPA has treatment data from more than one technology following the screening activity, EPA uses the statistical method known as analysis of variance (ANOVA) to determine if one technology performs significantly better. This statistical method (summarized in Appendix A) provides a measure of the differences between two data sets. If EPA finds that one technology performs significantly better (i.e., the data sets are not homogeneous), BOAT treatment standards are the level of performance achieved by the best technology multiplied by the corresponding variability factor for each regulated constituent. If the differences in the data sets are not statistically significant, the data sets are said to be homogeneous. Specifically, EPA uses the analysis of variance to determine 1-37 Rev. 3 ------- whether BOAT represents a level of performance achieved by only one technology or represents a level of performance achieved by more than one (or all) of the technologies. If the Agency finds that the levels of performance for one or more technologies are not statistically different, EPA averages the performance values achieved by each technology and then multiplies this value by the largest variability factor associated with any of the acceptable technologies. A detailed discussion of the treatment selection method and an example of how EPA chooses BOAT from multiple treatment systems is provided in Appendix A. (3) Quality Assurance/Quality Control. This section presents the principal quality assurance/quality control (QA/QC) procedures employed in screening and adjusting the data to be used in the calculation of treatment standards. Additional QA/QC procedures used in collecting and screening data for the BOAT program are presented in EPA's Generic Quality Assurance Project Plan for Land Disposal Restrictions Program ("BOAT") (EPA/530-SW-87-001, March 1987). To calculate the treatment standards for the Land Disposal Restriction Rules, it is first necessary to determine the recovery value for each constituent (the amount of constituent V recovered after spiking, which is the addition of a known amount of the constituent, minus the initial concentration in the samples divided by the amount added) for a spike of the treated 1-38 Rev. 3 ------- residual. Once the recovery value is determined, the following procedures are used to select the appropriate percent recovery value to adjust the analytical data: (a) If duplicate spike recovery values are available for the constituent of interest, the data are adjusted by the lowest available percent recovery value (i.e., the value that will yield the most conservative estimate of treatment achieved). However, if a spike recovery value of less than 20 percent is reported for a specific constituent, the data are not used to set treatment standards because the Agency does not have sufficient confidence in the reported value to set a national standard. (b) If data are not available for a specific constituent but are available for an isomer, then the spike recovery data are transferred from the isomer and the data are adjusted using the percent recovery selected according to the procedure described in (a) above. (c) If data are not available for a specific constituent but are available for a similar class of constituents (e.g., volatile organics, acid-extractable semivolatiles), then spike recovery data available for this class of constituents are transferred. All spike recovery values greater than or equal to 20 percent for a spiked sample are averaged and the constituent concentration is adjusted by the average recovery value. If spiked recovery data are available for more than one sample, the average is calculated for each sample and the data are adjusted by the lowest average value. (d) If matrix spike recovery data are not available for a set of data to be used to calculate treatment standards, then matrix spike recovery data are transferred from a waste that the Agency believes is a similar matrix (e.g., if the data are for an ash from incineration, then data from other incinerator ashes could be used). While EPA recognizes that transfer of matrix spike recovery data from a similar waste is not an exact analysis, this is considered the best approach for adjusting the data to account for the fact that most analyses do not result in extraction of 100 percent of the constituent. In assessing the recovery 1-39 Rev. 3 ------- data to be transferred, the procedures outlined in (a), (b), and (c) above are followed. The analytical procedures employed to generate the data used to calculate the treatment standards are listed in Appendix E of this document. In cases where alternatives or equivalent procedures and/or equipment are allowed in EPA's SW-846, Third Edition (November 1986) methods, the specific procedures and equipment used are also documented in this Appendix. In addition, any deviations from the SW-846, Third Edition, methods used to analyze the specific waste matrices are documented. It is important to note that the Agency will use the methods and procedures delineated in Appendix E to enforce the treatment standards presented in Section 6 of this document. Accordingly, facilities should use these procedures in assessing the performance of their treatment systems. 1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes (1) Wastes from Treatment Trains Generating Multiple Residues. In a number of instances, the proposed BOAT consists of a series of operations each of which generates a waste residue. For example, the proposed BDATvfor a certain waste code is based on solvent extraction, steam stripping, and activated carbon adsorption. Each of these treatment steps generates a waste requiring treatment — a solvent-containing stream from 1-40 Rev. 3 ------- solvent extraction, a stripper overhead, and spent activated carbon. Treatment of these wastes may generate further residues; for instance, spent activated carbon (if not regenerated) could be incinerated, generating an ash and possibly a scrubber water waste. Ultimately, additional wastes are generated that may require land disposal. With respect to these wastes, the Agency wishes to emphasize the following points: (a) All of the residues from treating the original listed wastes are likewise considered to be the listed waste by virtue of the derived-from rule contained in 40 CFR Part 261.3(c)(2). (This point is discussed more fully in (2) below.) Consequently, all of the wastes generated in the course of treatment would be prohibited from land disposal unless they satisfy the treatment standard or meet one of the exceptions to the prohibition. (b) The Agency's proposed treatment standards generally contain a concentration level for wastewaters and a concentration level for nonwastewaters. The treatment standards apply to all of the wastes generated in treating the original prohibited waste. Thus, all solids generated from treating these wastes would have to meet the treatment standard for nonwastewaters. All derived-from wastes meeting the Agency definition of wastewater (less than 1 percent TOC and less than 1 percent total filterable solids) would have to meet the treatment standard for wastewaters. EPA wishes to make clear that this approach is not meant to allow partial treatment in order to comply with the applicable standard. (c) The Agency has not performed tests, in all cases, on every waste that can result from every part of the treatment train. However, the Agency's treatment standards are based on treatment of the most concentrated form of the waste. Consequently, the Agency believes that the less concentrated wastes generated in the course of treatment will also be able to be treated to meet this value. 1-41 Rev. 3 ------- (2) Mixtures and Other Derived-From Residues. There is a further question as to the applicability of the BOAT treatment standards to residues generated not from treating the waste (as discussed above), but from other types of management. Examples are contaminated soil or leachate that is derived from managing the waste. In these cases, the mixture is still deemed to be the listed waste, either because of the derived-from rule (40 CFR Part 261.3(c)(2)(i)) or the mixture rule (40 CFR Part 261.3(a)(2)(iii) and (iv) or because the listed waste is contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The prohibition for the particular listed waste consequently applies to this type of waste. The Agency believes that the majority of these types of residues can meet the treatment standards for the underlying listed wastes (with the possible exception of contaminated soil and debris for which the Agency is currently investigating whether it is appropriate to establish a separate treatability subcategorization). For the most part, these residues will be less concentrated than the original listed waste. The Agency's treatment standards also make a generous allowance for process variability by assuming that all treatability values used to establish the standard are lognormally distributed. The waste y also might be amenable to a relatively nonvariable form of treatment technology such as incineration. Finally, and perhaps most important, the rules contain a treatability variance that 1-42 Rev. 3 ------- allows a petitioner to demonstrate that its waste cannot be treated to the level specified in the rule (40 CFR Part 268.44(a). This provision provides a safety valve that allows persons with unusual waste matrices to demonstrate the appropriateness of a different standard. The Agency, to date, has not received any petitions under this provision (for example, for residues contaminated with a prohibited solvent waste), indicating, in the Agency's view, that the existing standards are generally achievable. (3) Residues from Managing Listed Wastes or that Contain Listed Wastes. The Agency has been asked if and when residues from managing hazardous wastes, such as leachate and contaminated ground water, become subject to the land disposal prohibitions. Although the Agency believes this question to be settled by existing rules and interpretative statements, to avoid any possible confusion the Agency will address the question again. Residues from managing First Third wastes, listed California List wastes, and spent solvent and dioxin wastes are all considered to be subject to the prohibitions for the underlying hazardous waste. Residues from managing California List wastes likewise are subject to the California List prohibitions when the residues themselves exhibit a characteristic of hazardous waste. This determination stems directly from the derived-from rule in 40 CFR Part 261.3(c)(2) or in some cases from the fact that the 1-43 Rev. 3 ------- waste is mixed with or otherwise contains the listed waste. The underlying principle stated in all of these provisions is that listed wastes remain listed until delisted. The Agency's historic practice in processing delisting petitions addressing mixing residuals has been to consider them to be the listed waste and to require that delisting petitioners address all constituents for which the derived-from waste (or other mixed waste) was listed. The language in 40 CFR Part 260.22(b) states that mixtures or derived-from residues can be delisted provided a delisting petitioner makes a demonstration identical to that which a delisting petitioner would make for the underlying waste. These residues consequently are treated as the underlying listed waste for delisting purposes. The statute likewise takes this position, indicating that soil and debris that are contaminated with listed spent solvents or dioxin wastes are subject to the prohibition for these wastes even though these wastes are not the originally generated waste, but rather are a residual from management (RCRA section 3004(e)(3)). It is EPA's view that all such residues are covered by the existing prohibitions and treatment standards for the listed hazardous waste that these residues contain and from which they are derived. 1-44 Rev. 3 ------- 1.2.8 Transfer of Treatment Standards EPA is proposing some treatment standards that are not based on testing of the treatment technology of the specific waste subject to the treatment standard. Instead, the Agency has determined that the constituents present in the subject waste can be treated to the same performance levels as those observed in other wastes for which EPA has previously developed treatment data. EPA believes that transferring treatment performance for use in establishing treatment standards for untested wastes is valid technically in cases where the untested wastes are generated from similar industries, similar processing steps, or have similar waste characteristics affecting performance and treatment selection. Transfer of treatment standards to similar wastes or wastes from similar processing steps requires little formal analysis. However, in the case where only the industry is similar, EPA more closely examines the waste characteristics prior to concluding that the untested waste constituents can be treated to levels associated with tested wastes. EPA undertakes a two-step analysis when determining whether wastes generated by different processes within a single industry can be treated to the same level of performance. First, EPA reviews the available waste characteristic data to identify those parameters that are expected to affect treatment selection. EPA has identified some of the most important constituents and other 1-45 Rev. 3 ------- parameters needed to select the treatment technology appropriate for a given waste. A detailed discussion of each analysis, including how each parameter was selected for each waste, can be found in the background document for each waste. Second, when an individual analysis suggests that an untested waste can be treated with the same technology as a waste for which treatment performance data are already available, EPA analyzes a more detailed list of constituents that represent some of the most important waste characteristics that the Agency believes will affect the performance of the technology. By examining and comparing these characteristics, the Agency determines whether the untested wastes will achieve the same level of treatment as the tested waste. Where the Agency determines that the untested waste is easier to treat than the tested waste, the treatment standards can be transferred. A detailed discussion of this transfer process for each waste can be found in later sections of this document. 1.3 Variance from the BOAT Treatment Standard The Agency recognizes that there may exist unique wastes that cannot be treated to the level specified as the treatment standard. In such a case, a generator or owner/operator may submit a petition to the Administrator requesting a variance from the treatment standard. A particular waste may be significantly 1-46 Rev. 3 ------- different from the wastes considered in establishing treatability groups because the waste contains a more complex matrix that makes it more difficult to treat. For example, complex mixtures may be formed when a restricted waste is mixed with other waste streams by spills or other forms of inadvertent mixing. As a result, the treatability of the restricted waste may be altered such that it cannot meet the applicable treatment standard. Variance petitions must demonstrate that the treatment standard established for a given waste cannot be met. This demonstration can be made by showing that attempts to treat the waste by available technologies were not successful or by performing appropriate analyses of the waste, including waste characteristics affecting performance, which demonstrate that the waste cannot be treated to the specified levels. Variances will not be granted based solely on a showing that adequate BDAT treatment capacity is unavailable. (Such demonstrations can be made according to the provisions in Part 268.5 of RCRA for case-by-case extensions of the effective date.) The Agency will consider granting generic petitions provided that representative data are submitted to support a variance for each facility covered by the petition. 1-47 Rev. 3 ------- Petitioners should submit at least one copy to: The Administrator U.S. Environmental Protection Agency 401 M Street, S.W. Washington, DC 20460 An additional copy marked "Treatability Variance" should be submitted to: Chief, Waste Treatment Branch Office of Solid Waste (WH-565) U.S. Environmental Protection Agency 401 M Street, S.W. Washington, DC 20460 Petitions containing confidential information should be sent with only the inner envelope marked "Treatability Variance" and "Confidential Business Information" and with the contents marked in accordance with the requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by 43 FR 4000). The petition should contain the following information: (1) The petitioner's name and address. (2) A statement of the petitioner's interest in the proposed action. (3) The name, address, and EPA identification number of the facility generating the waste, and the name and telephone number of the plant contact. v (4) The process(es) and feed materials generating the waste and an assessment of whether such process(es) or feed materials may produce a waste that is not covered by the demonstration. 1-48 Rev. 3 ------- (5) A description of the waste sufficient for comparison with the waste considered by the Agency in developing BOAT, and an estimate of the average and maximum monthly and annual quantities of waste covered by the demonstration. (Note: The petitioner should consult the appropriate BOAT background document for determining the characteristics of the wastes considered in developing treatment standards.) (6) If the waste has been treated, a description of the system used for treating the waste, including the process design and operating conditions. The petition should include the reasons the treatment standards are not achievable and/or why the petitioner believes the standards are based on inappropriate technology for treating the waste. (Note: The petitioner should refer to the BDAT background document as guidance for determining the design and operating parameters that the Agency used in developing treatment standards.) (7) A description of the alternative treatment systems examined by the petitioner (if any); a description of the treatment system deemed appropriate by the petitioner for the waste in question; and, as appropriate, the concentrations in the treatment residual or extract of the treatment residual (i.e., using the TCLP where appropriate for stabilized metals) that can be achieved by applying such treatment to the waste. (8) A description of those parameters affecting treatment selection and waste characteristics that affect performance, including results of all analyses. (See Section 3.0 for a discussion of waste characteristics affecting performance that the Agency has identified for the technology representing BDAT.) (9) The dates of the sampling and testing. (10) A description of the methodologies and equipment used to obtain representative samplevs. (11) A description of the sample handling and preparation techniques, including techniques used for extraction, containerization, and preservation of the samples. 1-49 Rev. 3 ------- (12) A description of analytical procedures used including QA/QC methods. After receiving a petition for a variance, the Administrator may request any additional information or waste samples that may be required to evaluate and process the petition. Additionally, all petitioners must certify that the information provided to the Agency is accurate under 40 CFR Part 268.4(b). In determining whether a variance will be granted, the Agency will first look at the design and operation of the treatment system being used. If EPA determines that the technology and operation are consistent with BOAT, the Agency will evaluate the waste to determine if the waste matrix and/or physical parameters are such that the BOAT treatment standards reflect treatment of this waste. Essentially, this latter analysis will concern the parameters affecting treatment selection and waste characteristics affecting performance parameters. In cases where BOAT is based on more than one technology, the petitioner will need to demonstrate that the treatment standard cannot be met using any of the technologies, or that none of the technologies are appropriate,for treatment of the waste. After the Agency has made a determination on the petition, the Agency's findings will be published in the Federal Register, followed by a 30-day period for public comment. 1-50 Rev. 3 ------- After review of the public comments, EPA will publish its final determination in the Federal Register as an amendment to the treatment standards in 40 CFR Part 268, Subpart D. 1-51 Rev. 3 ------- 2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION The previous section provided the background for the Agency's study of K103 and K104 wastes. The purpose of this section is to describe the industry that will be affected by land disposal restrictions on waste codes K103 and K104, and to characterize these wastes. This section includes a description of the industry affected, the production processes employed in this industry, and a discussion of how K103 and K104 wastes are generated by these processes. The section concludes with a characterization of the K103 and K104 waste streams, and a determination of the waste treatability group for these wastes. The full list of hazardous waste codes from specific sources is given in 40 CFR 261.32 (see discussion in Section 1 of this document). Within this list, two specific hazardous waste codes are generated by the aniline/nitrobenzene industry: K103: Process residues from aniline extraction from the production of aniline (basis for listing: aniline, nitrobenzene, phenylenediamine). K104: Combined wastewater streams generated from nitrobenzene/aniline production (basis for listing: aniline, benzene, diphenylamine, nitrobenzene, phenylenediamine). The Agency has determined that these waste codes (K103 and K104) represent a separate waste treatability group. This was established because industry processes are similar; therefore, 2-1 Rev. 3 ------- the wastes are expected to have similar physical and chemical characteristics (see Section 1 for a discussion of waste treatability groups). In addition, these wastes are frequently mixed in industry prior to treatment. As a result, the Agency has examined the sources of the wastes, applicable treatment technologies, and treatment performance attainable in order to support a single regulatory approach for the two wastes. 2.1 Industry Affected and Process Description The four digit standard industrial classification (SIC) code reported for the aniline/nitrobenzene industry is 2869. The Agency estimates that six facilities in the United States are actively involved in aniline production which could generate K103. Four of these facilities are actively co-producing aniline and nitrobenzene, and could generate K104 waste. Information from trade associations provide a geographic distribution of the number of these facilities across the United States. Tables 2-1 and 2-2 present the location of those facilities which may generate waste codes K103 and K104 in each state and in each EPA region. As can be seen in Tables 2-1 and 2-2, these facilities are concentrated in the central and eastern V states (EPA Regions III through VI). Figure 2-1 illustrates this data plotted on a map of the United States. 2-2 Rev. 3 ------- Table 2-1 Facilities Producing K103 and K104 State (EPA Region) Louisiana (VI) Mississippi (IV) North Carolina (IV) Ohio (V) Texas (VI) West Virginia (III) Total Number of Facilities 1 1 1 1 1 1 6 Reference: SRI Chemical Economics Handbook, 1985 Table 2-2 Facilities Producing K103 and K104 EPA Rea ion III IV V VI Number of Facilities 1 2 1 2 Total 6 Reference; SRI Chemical Economics Handbook, 1985. Nitrobenzene is manufactured by either liquid or vapor phase nitration of benzene. The liquid phase nitration process is reported to be the more prevalent of the two processes used to manufacture nitrobenzene. In liquid phase nitration, benzene is nitrated in a reactor with an aqueous mixture of sulfuric acid and nitric acid (see Figure 2-2). Crude .nitrobenzene is formed, and is separated from the reactants and by-products by a series of purification steps. 2-3 Rev. 3 ------- O o LU DC a. LU Q LU CO fa s CO o O o Q o DC Q_ CO LU O < I ------- NITRIC ACID SODIUM HYDROXIDE NITROBENZENE PRODUCT K103 FROM SEPARATOR LIflUID/ LIBUID EXTRACTION TO FURTHER HASTEMATER TREATMENT PRODUCT ANILINE TO INCINERATOR SOURCE: DELISTING PETITION FOR WASTE STREAM K104 - COMBINED WASTEWATER STREAMS GENERATED FROM NITROBENZENE/ANILINE PRODUCTION. PETITION NO. 0312. FIGURE 2-2 GENERATION OF K103 AND K104 FROM NITROBENZENE/ANILINE PRODUCTION (LIQUID PHASE NITRATION OF BENZENE AND LIQUID PHASE REDUCTION OF NITROBENZENE) 2-5 Rev. 3 ------- In the initial nitrobenzene purification step, the product stream from the reactor enters a separator where it is cooled and allowed to settle and to separate by gravity into an organic and an aqueous phase. The aqueous phase, consisting mainly of untreated sulfuric and nitric acid, goes to the denitrator where fresh benzene is added to remove trace amounts of nitric acid. The benzene and trace amounts of nitrobenzene, formed in the denitrator, are returned to the nitrobenzene reactor. The acid phase from the denitrator is sent to the waste acid stripper for acid recovery by volatilization. The recovered acid from the waste acid stripper is recycled through an acid concentrator to the reactor. The organic phase from the separator, consisting mainly of nitrobenzene, is washed with water in a prewasher and with caustic soda in a washer to remove traces of acid. The washwater streams from the prewasher and washer are both sent to a wastewater extractor where nitrobenzene is recovered from the washwater (or wastewater). In the final purification step, the nitrobenzene stream from the washer is distilled in the nitrobenzene topping column to produce a high purity nitrobenzene product. V Aniline is produced by reducing nitrobenzene with hydrogen in the presence of a catalyst. The three alternative reduction processes currently in use are as follows: catalytic vapor 2-6 Rev. 3 ------- phase, catalytic liquid phase, and dissolving metal (or Bechamp) process. Most of the aniline in the United States is reported to be produced by the catalytic vapor phase and catalytic liquid phase processes. In the catalytic liquid phase process, nitrobenzene is reduced by hydrogen to form aniline in the presence of a nickel catalyst in a reactor (see Figure 2-2). The crude aniline from the reactor is separated from water and other by-products in a two-stage gravity decantation process consisting of a crude aniline separator and a separator. The water phases from both separators are combined and sent to the aniline liquid/liquid extractor which recovers aniline from the residual wastewater stream. The aniline stream from the crude aniline separator is distilled in a rectification column to produce a high purity aniline product. The listed wastes K103 and K104 are generated in the manufacture of aniline and aniline/nitrobenzene, respectively. The generation of these wastes is discussed further in Sections 2.1.1 and 2.1.2. 2.1.1 Generation of K103 Waste «• The listed waste K103 is generated in the production of aniline in both the crude aniline separator and in the 2-7 Rev. 3 ------- aniline/water separator after the rectifier column. In the crude aniline separator (see Figure 2-2), the product stream from the aniline reactor is cooled and allowed to settle and separate by gravity into an organic and an aqueous phase. The aqueous phase, which is the listed waste K103, is pumped to the aniline liquid/liquid extractor. The bottoms stream from the rectifier column that purifies the crude aniline enters a purge recovery column which separates water and aniline by distillation. The aniline-containing stream from the purge recovery columns enters a separator where it is cooled and allowed to settle and separate by gravity into an organic and an aqueous phase. The organic phase, consisting mainly of aniline, is recycled to the aniline reactor. The aqueous phase, which is the listed waste K103, is combined with the aqueous phase from the crude aniline separator and pumped to the aniline liquid/liquid extractor. The bottoms from the purge recovery column are stored in the tars tank and eventually incinerated. 2.1.2 Generation of K104 Waste The listed waste K104 is generated in the production of V nitrobenzene at both the prewasher and the washer (see Figure 2-2). In the prewasher, water is used to remove acid from the nitrobenzene stream coming from the separator by exploiting 2-8 Rev. 3 ------- the relatively high solubility of the acids in water. An organic phase, consisting mainly of nitrobenzene, is separated from the aqueous phase in the prewasher and is sent to the washer. The aqueous phase from the prewasher, which is the listed waste K104, is sent to the nitrobenzene liquid/liquid extractor. In the washer, caustic soda is used to neutralize remaining traces of acid in the nitrobenzene stream from the prewasher. As before, organic and aqueous phases are formed by settling and gravity separation. Nitrobenzene is removed with the organic phase from the washer and enters the nitrobenzene topping column. The aqueous phase from the washer, which is the listed waste K104, is combined with the aqueous phase from the prewasher and enters the nitrobenzene liquid/liquid extractor. Other wastewater streams from the co-production of nitrobenzene and aniline are also considered to be K104, if they are not mixed with the wastewater streams from the prewasher and washer. These streams include the overhead stream from the waste acid stripper and the wastewater stream from the aniline liquid/liquid extractor. 2.2. Waste Characterization * This section includes all waste characterization data available to the Agency for the K103 and K104 waste treatability group. An estimate of the major constituents which comprise each 2-9 Rev. 3 ------- waste and their approximate concentrations is presented in Table 2-3. The percent concentration of each major constituent in the waste was determined from best estimates based on chemical analyses. Table 2-3 shows that the major constituent of both K103 and K104 is water (at >94.7% and >98.7%, respectively). The primary organic BOAT constituent in K103 is aniline, with benzene and sulfide being the other primary BOAT constituents present (<1.0%). The primary organic BOAT constituent in K104 is nitrobenzene, with benzene and cyanides being the other primary BOAT constituents present (<1.0%). The ranges of BOAT constituents present in each waste and all other available data concerning waste characterization parameters obtained from the Onsite Engineering report for E. I. duPont de Nemours, Beaumont, Texas, are presented by waste code in Table 2-4. This table lists the levels of BOAT organics (volatile and semivolatile), metals, and inorganics present in K103 and K104 wastes. Other parameters analyzed in the wastes include: total dissolved solids, total suspended solids, total organic carbon, and chemical oxygen demand. Tables 2-3 and 2-4 together provide a thorough characterization of K103 and K104 wastes. 2-10 Rev. 3 ------- Table 2-3 Major Constituent Composition for K103 and K104 Wastes* Constituent Water Aniline BDAT Constituents (Other than Aniline) Total K103 Waste Concentration (Wt. Percent) >94.7 4.3 100.0% Constituent Water Nitrobenzene BDAT Constituents (Other than Nitrobenzene) Total K104 Waste Concentration (Wt. Percent) >98.7 0.3 100.0 * Percent concentrations presented here were determined from best estimates based on chemical analyses. Reference; Onsite Engineering Report for E. I. duPont de Nemours, Beaumont, Texas. Pages 6 and 8. 2-11 Rev. 3 ------- TABLE 2-4 BOAT CONSTITUENT ANALYSIS AND OTHER DATA Untreated Waste Conentration Range, ppm* BOAT ORGANICS K103 K104 Volatile 4. Benzene 32-81 4.5 - 320 Semi volatile 56. Aniline 33,000 - 53,000 <150 - <300 101. 2,4-Dinitrophenol <7,500 - <15,000 750 - <1,500 126. Nitrobenzene 1,900 - 2,800** 2,200 - 3,900 142. Phenol 1,500 - <3,000 <150 - <300 BOAT Metals 155. Arsenic 0.01 - 21 <0.01 156. Barium <.001 .0015 - .017 159. Chromium <.007 <.007 - .432 160. Copper <.006 <.006 - .012 161. Lead <.005 - 6 <.020 163. Nickel <.011 <.011 - .238 168. Zinc 3 - 21 <.038 - .079 BOAT Inorganics 169. Total Cyanides <0.010 - 0.075 3.06 - 6.28 171. Sulfide 62 - 89 <1.0 Other Parameters Total Dissolved Solds Total Suspended Solids Total Organic Carbon Chemical Oxygen Demand + 8 - 24 33,500 - 36,300 97,800 - 111,000 10,200 - 27,200 21 - 172 1,420 - 2,990 5,290 - 48,200 * - Values obtained from Onsite Engineering Report of Treatment Technology Performance for E. I. du Pont de Nemours, Inc., Beaumont, Texas. Tables 6-6 and 6-8. + - Total dissolved solids could not be analyzed since the sample flashed before an analysis could be completed. This was due to the amount of organics contained in the sample. ** - Value represents the treated waste from the aniline liquid/liquid extractor. Nitrobenzene was used as a solvent in the aniline liquid/liquid extractor. 2-12 Rev. 3 ------- 2.3 Determination of Waste Treatability Group Fundamental to waste treatment is the concept that the type of treatment technology used and the level of treatment achieved depend on the physical and chemical characteristics of the waste. In cases where EPA believes that wastes represented by different codes can be treated to similar concentrations using the same technologies, the Agency combines the codes into one treatability group. In particular, the two listed wastes (K103 and K104) from the production of aniline and nitrobenzene were combined into a single waste treatability group. These two wastes are produced in the aniline/nitrobenzene industry and are frequently treated together in the industry using a single waste treatment technology. Also, the two wastes have similar physical and chemical characteristics including: high water content, high BDAT organic levels (benzene and aniline or nitrobenzene), relatively low levels of BDAT metals and inorganics, and low filterable solids content. For these reasons, the Agency believes that the K103 and K104 wastes represent a separate waste treatability group. 2-13 Rev. 3 ------- 3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES The purpose of this section is to describe applicable treatment technologies for treatment of K103 and K104 wastes that the Agency has identified as applicable and to describe which of the applicable technologies the Agency has determined to be demonstrated. Included in this section are discussions of those applicable treatment technologies that have been demonstrated on a commercial basis. The technologies which were considered to be applicable are those which treat organic compounds by concentration reduction. Also, this section describes the performance data available for these technologies. The previous section described the industry that will be affected by the land disposal restrictions on K103 and K104 wastes, and presented a characterization of these wastes. Analysis of the K103 wastewaters indicates that they primarily consist of water (94.7 percent) and aniline (4.3 percent). The K104 wastewater primarily consists of water (98.7 percent), nitrobenzene (0.3 percent) and small amounts of cyanides. The Agency has identified these treatment technologies which may be applicable to K103 and K104 because the technologies are designed to reduce the concentration of organic compounds present in the untreated waste. The selection of the treatment technologies applicable for treating organic compounds and cyanides in K103 3-1 Rev. 3 ------- and K104 wastewaters is based on information obtained from engineering site visits and available literature sources. 3.1 Applicable Treatment Technologies For K103 and K104 wastewaters, the Agency has identified the following treatment technologies as being applicable: liquid/liquid (or solvent) extraction which separates the organic components from the aqueous components by exploiting the relative differential or selective solubility of the organic constituents in a particular solvent; steam stripping, which removes organics from the liquid phase through volatilization; activated carbon adsorption which uses carbon granules to selectively remove organic contaminants by adsorption; and biological treatment which involves the use of microorganisms to degrade organic compounds. The use of activated carbon adsorption in treating the wastewaters generates a spent carbon which is nonwastewater. The Agency has identified rotary kiln incineration as being an applicable treatment technology for this nonwastewater form of K103 and K104. 3-2 Rev. 3 ------- 3.2 Demonstrated Treatment Technologies i. Nonwastewaters The demonstrated technology that the Agency has identified for treatment of K103 and K104 nonwastewaters is rotary kiln incineration. This technology has not been commercially demonstrated for the treatment of K103 and K104 nonwastewaters, but it has been demonstrated for wastes similar to K103 and K104 nonwastewaters. However, the Agency does not have performance data for this treatment technology. ii. Wastewaters The Agency has determined that all of the applicable technologies for wastewaters are demonstrated. The demonstrated treatment technologies listed above for K103 and K104 generally are combined to form treatment systems or treatment trains which are more effective than single technologies alone in removing and recovering organics from wastewater. The three treatment technology systems which are demonstrated or are currently in commercial use are as follows: o liquid/liquid extraction followed by steam stripping and activated carbon adsorption, o steam stripping followed by activated carbon adsorption, and o steam stripping followed by biological treatment. 3-3 Rev. 3 ------- A more detailed discussion of the treatment technology system for which the Agency has collected performance data is presented in Sections 3.2.1 through 3.2.3. 3.2.1 Solvent Extraction Solvent extraction is a treatment technology used to remove a constituent from a waste by mixing the waste with a solvent that is immiscible with the waste and in which the waste constituent of concern is preferentially soluble. Solvent extraction is commonly called liquid extraction or liquid-liquid extraction. EPA also uses this term to refer to extraction of BOAT list organics from a solid waste. When BOAT list metals are extracted using acids, EPA uses the term acid leaching. (1) Applicability and Use of Solvent Extraction Theoretically, solvent extraction has broad applicability in that it can be used for wastes that have high or low concentrations of a range of waste characteristics including total organic carbon, filterable solids, viscosity, and BOAT list metals content. The key to its use is whether the BOAT constituents can be extracted from the waste matrix containing the constituents of concern. For a waste matrix with high filterable solids this would mean that the solids could be land disposed following solvent extraction. For a predominately 3-4 Rev. 3 ------- liquid waste matrix with low filterable solids, the extracted liquid (referred to as the raffinate) could be reused. Solvent extraction can seldom be used without additional treatment (e.g., incineration) of the extract; however, some industries may be able to recycle the solvent stream contaminated with the BOAT constituents back to the process. (2) Underlying Principles of Operation For solvent extraction to occur, the BDAT constituents of concern in the waste stream must be preferentially soluble in the solvent and the solvent must be essentially immiscible with the waste stream. In theory, the degree of separation that can be achieved is provided by the selectivity value; this value is the ratio of the equilibrium concentration of the constituent in the solvent to the equilibrium concentration of the constituent in the waste. The solvent and waste stream are mixed to allow mass transfer of the constituent(s) from the waste stream to the solvent. The solvent and waste stream are then allowed to separate under quiescent conditions. The solvent solution, containing the extracted contaminant is called the extract. The extracted waste stream with the contaminants removed is called the raffinate. The simplest extraction system comprises three components: (1) the solute, or the contaminant to be extracted; 3-5 Rev. 3 ------- (2) the solvent; and (3) the nonsolute portion of the waste stream. For simple extractions, solute passes from the waste stream to the solvent phase. A density difference exists between the solvent and waste stream phases. The extract can be either the heavy phase or the light phase. (3) Physical Description of a Solvent Extraction Process The simplest method of extraction is a single stage system. The solvent and waste stream are brought together; clean effluent and solvent are recovered without further extraction. The clean effluent is referred to as the raffinate, and the solvent containing the constituents that were removed from the waste stream are known as the extract. The amount of solute extracted is fixed by equilibrium relations and the quantity of solvent used. Single stage extraction is the least effective extraction system. Another method of extraction is simple multistage contact extraction. In this system, the total quantity of solvent to be used is divided into several portions. The waste stream is contacted with each of these portions of fresh solvent in a series of successive steps or stages. Raffinate from the first V extraction stage is contacted with fresh solvent in a second stage, and so on. 3-6 Rev. 3 ------- In counter-current, multistage contact, fresh solvent and the waste stream enter at opposite ends of a series of extraction stages. Extract and raffinate layers pass continuously and countercurrently from stage to stage through the system. In order to achieve a reasonable approximation of phase equilibrium, solvent extraction requires the intimate contacting of the phases. Several types of extraction systems are used for contact and separation; two of these, mixer-settler systems and column contactors, are discussed below. i. Mixer-Settler Systems Mixer-settler systems are comprised of a mixing chamber for phase dispersion, followed by a settling chamber for phase separation. The vessels may be either vertical or horizontal. Dispersion in the mixing chamber occurs by pump circulation, nonmechanical in-line mixing, air agitation, or mechanical stirring. In a two-stage mixer-settler system the dispersed phase separates in a horizontal settler. The extract from the second settler is recycled to the first settler (see Figure 3-1). Extract properties such as density or specific constituent concentration may be monitored to determine when the extract must be sent to solvent recovery and fresh or regenerated solvent > added to the system. Mixer-settler systems can handle solids or highly viscous liquids. Design scaleup is reliable, and mixer-settlers can handle difficult dispersion systems. Intense 3-7 Rev. 3 ------- LU U_ U. SOLVENT FROM o LU 0 O LU or / FRESH SOLVENT a: LU a. > Z> O LU CJ :>£ LU y ^^ y > y LU cn H-l^ !.!_ CD 1 ECYCLED JLVENT ac cn f \ i— o ac i— X LU • ^ IACT TO RECOVERY u. X UJ CE LU 1 a- >- m £ co LU ^ Z ac !^ o ID ^- i—i Sg^ 11 (-u pp "- ------- agitation to provide high rates of inass transfer can produce solvent-feed dispersions that are difficult to separate into distinct phases. ii. Column Contactors Packed and sieve-tray are two different types of column contactors that do not require mechanical agitation. Figure 3-2 presents schematics of the two types of extraction columns. A packed extractor contains packing materials, such as saddles, rings, or structured packings of gauze or mesh. Mass transfer of the solute to the extract is promoted because of breakup and distortion of the dispersed phase as it contacts the packing. The sieve-tray extractor is similar to a sieve-tray column used in distillation. Tray perforations result in the formation of liquid droplets to aid the mass transfer process. The improved transfer is accomplished by the fact that the droplets allow for more intimate contact between extract and raffinate. (4) Waste Characteristics Affecting Performance V In determining whether solvent extraction is likely to achieve the same level of performance on an untested waste as a previously tested waste, the Agency will focus on the waste 3-9 Rev. 3 ------- SB 85 •< a: CE o i— i— o LU CE LU f— H X CO LU OQ •< I— t—t CD ------- characteristics that provide an estimate of the selectivity value previously described. EPA believes that the selectivity value can best be estimated by analytically measuring the partitioning coefficients of the waste constituents of concern and the solubility of the waste matrix in the extraction solvent. Accordingly, EPA will use partitioning coefficients and solubility of the waste matrix as surrogates for the selectivity value in making decisions regarding transfer of treatment standards. For the liquid/liquid extraction system, the WCAPs are the relative solubilities which is a measure of the partitioning coefficient, of the various waste constituents in water and in nitrobenzene. The primary organic constituents of K103 and K104 (benzene, aniline, nitrobenzene, phenol, and 2,4-dinitrophenol), along with cyanides, are all soluble in nitrobenzene at 40°C. Phenol and cyanides are soluble in water at 40°C, while benzene, aniline, and nitrobenzene are relatively insoluble in water (0.137 g/100 g H20saturated solution at 54.5°C). It should also be noted that the density of nitrobenzene relative to water is 1.205 at 4°C. 3-11 Rev. 3 ------- (5) Design and Operating Parameters EPA's analysis of whether a solvent extraction system is well designed will focus on whether the BOAT list constituents are likely to be effectively separated from the waste. The particular design and operating parameters to be evaluated are: (1) the selection of a solvent, (2) equilibrium data, (3) temperature and pH, (4) mixing, and (5) settling time. (1) The selection of a solvent. In assessing the design of a solvent extraction system, the most important aspect to evaluate is the solvent used and the basis on which the particular solvent was selected. Solvent selection is important because, as indicated previously, different waste constituents of concern will have different solubilities in various solvents, and it is the extent to which the waste constituents are preferentially soluble in the selected solvent that determines the effectiveness of this technology. In addition to this information, EPA would also want to review any empirical extraction data used to design the system. (2) Equilibrium Data. For solvent extraction systems that are operated in a continuous mode, the extraction process will generally be conducted using a series of equilibrium stages as discussed previously. The number of equilibrium stages and the associated flow rates of the waste and solvent will be based on 3-12 Rev. 3 ------- empirical equilibrium data. EPA will evaluate these data as part of assessing the design of the system. (3) Temperature and pH. Temperature and pH changes can affect equilibrium conditions and, consequently, the performance of the extraction system. Thus, EPA would attempt to monitor and record these values on a continuous basis. (4) Mixing. For mixer-settler type extraction processes, mixing determines the amount of contact between the two immiscible phases and, accordingly, the degree of mass transfer of the constituents to be extracted. EPA would thus want to know the type of mixers used and the basis for determining that this system would provide sufficient mixing. (5) Settling Time. For batch systems, adequate settling time must be allowed to ensure that separation of the phases has been completed. Accordingly, in assessing the design of a system, EPA would want to know settling time allowed and the basis for selection. 3-13 Rev. 3 ------- 3.2.2 Steam Stripping Steam stripping is a technology which can separate more volatile materials from less volatile materials by a process of vaporization and condensation. As such, it is a type of distillation process. (1) Applicability and Use of Technology Steam stripping is applicable to wastewaters that contain BOAT organics that are sufficiently volatile such that they can be removed by the application of steam. Waste parameters affecting treatment selection are filterable solids, total organic carbon (TOC), and the presence of BDAT organics that are either not volatile or only minimally volatile. (2) Underlying Principles of Operation The basic principle of operation for steam stripping is the volatilization of hazardous constituents through the application of heat. The constituents that are volatilized are then condensed and either reused or further treated by liquid injection incineration. An integral part of the theory of steam stripping is the principle of vapor-liquid equilibrium. When a liquid mixture of two or more components is heated, a vapor phase is created above 3-14 Rev. 3 ------- the liquid phase. The vapor phase will be more concentrated in the constituents having the higher vapor pressure. If the vapor phase above the liquid phase is cooled to yield a condensate, a partial separation of the components results. The degree of separation would depend on the relative differences in the vapor pressures of the constituents; the larger the difference in the vapor pressure, the easier the separation can be accomplished. If the difference between the vapor pressure is extremely large, a single separation cycle or single equilibrium stage of vaporization and condensation may achieve a significant separation of the constituents. If the difference between the vapor pressures are small, then multiple equilibrium stages are needed to achieve effective separation. In practice, the multiple equilibrium stages are obtained by stacking trays or placing packing into a column. The vapor phase from a tray rises to the tray above it and the liquid phase falls to the tray below it. Essentially, each tray represents one equilibrium stage. In a packed steam stripping column, the individual equilibrium stages are not discernible, but the number of equivalent trays can be calculated from mathematical relationships. The vapor liquid equilibrium is expressed as relative volatility or the ratio of the vapor to liquid concentration for a constituent divided by the ratio of the vapor to liquid concentration of the other constituent. The relative volatility 3-15 Rev. 3 ------- is a direct measure of the ease of separation. If the numerical value is 1, then separation is impossible because the constituents have the same concentrations in the vapor and liquid phases. Separation becomes easier as the value of the relative volatility becomes increasingly greater than unity. (3) Physical Description of the Process A steam stripping unit consists of a boiler, a stripping section, a condenser, and a collection tank as shown by Figure 3-3. The boiler provides the heat required to vaporize the liquid fraction of the waste. The stripping section is composed of a set of trays or packing in a vertical column. The feed enters at the top. The stripping process uses multiple equilibrium stages, with the initial waste mixture entering the uppermost equilibrium stage. The boiler is located below the lowermost equilibrium stage so that vapor generated moves upward in the column coming into contact with the falling liquid. As the vapor comes into contact with the liquid at each stage, the more volatile components are removed or "stripped" from the liquid by the vapor phase. The concentration of the emerging vapor is slightly V enriched (as it is in equilibrium with the incoming liquid), and the liquid exiting the bottom of the boiler ("bottoms") is considerably enriched in the lower vapor pressure constituent(s). 3-16 Rev. 3 ------- HASTE INFLUENT VENT OF NON-CONDENSED VAPORS A CONDENSER TREATED EFFLUENT RECIEVER RECOVERED SOLVENT FOR REUSE OR TREATMENT FIGURE 3-3 STEAM STRIPPING 3-17 Rev. 3 ------- The process of stripping is very effective for wastewaters where the relative volatilities are large between the organics of concern and wastewater. Steam stripping is used to strip the organic volatiles from wastewater. The water effluent from the bottom of the stripper is reduced in organic content, but in some circumstances may require additional treatment, such as carbon adsorption or biological treatment. The steam and organic vapors leaving the top of the column are condensed. Organics in the condensate that form a separate phase in water usually can be separated and recovered or disposed of in a liquid injection incinerator. After separation the aqueous condensate is usually recycled to the stripper. (4) Waste Characteristics Affecting Performance In determining whether steam stripping is likely to achieve the same level of performance on an untested waste as a previously tested waste, EPA will focus on the following characteristics: boiling point, total dissolved solids, total dissolved volatile solids, and oil and grease. EPA recognizes these characteristics have some limitations in assessing transfer of performance; nevertheless, the Agency believes that they provide the best possible indicator of the preferred waste » characteristic analysis, i.e., relative volatility. Below is a discussion of relative volatility, as well as, EPA's rationale for evaluating the above described waste characteristics in 3-18 Rev. 3 ------- determining transfer of treatment performance. As discussed earlier, the term relative volatility ( OC ) refers to the ease with which a substance present in a solid or liquid waste will vaporize from that waste upon application of heat from an external source. Hence, it bears a relationship to the equilibrium vapor pressure of the substance. For an ideal binary mixture, the relative volatility ( o< ) is expressed as: Ki YiXi - SJ = Y^7 where K. and K. are equilibrium concentrations for components i and j respectively, Y is the mole fraction of the component in the vapor and X is the mole fraction of the component in the liquid. The term "ideal" refers to whether the vapor pressures of the two components can be linearly related to their respective compositions in the liquid phase; this,, is known as Raoult's law. In general, binary solutions at low pressures follow this law and are, therefore, "ideal"; most mixtures do not. 3-19 Rev. 3 ------- For non-ideal binary mixtures, the relative volatility ( is expressed as: ( = -- = -- x x KJ xi fi,v/ Xj fjjV where f is the fugacity. The term "fugacity" is a conveniently defined thermodynamic term to account for departures from ideal behavior of the gas and liquid; it can only be determined empirically. EPA recognizes that the relative volatilities can not be measured or calculated directly for the types of wastes generally treated by steam stripping even if these wastes behaved in an ideal manner. Determining relative volatilities is further complicated by the fact that the relative volatility changes as the temperature conditions change throughout the steam stripper. Accordingly, EPA will use the following surrogates: boiling point of the constituent, oil and grease content, total dissolved inorganic solids, and total dissolved volatile solids. For a given pressure and temperature, compounds with lower boiling points will have higher vapor pressures. Therefore, in the case of wastewaters containing low concentrations of organics where relative volatility is effectively a comparison of vapor pressures, the ratio of boiling points of the untested and tested constituents will indicate whether the untested waste can be treated to the same degree as the tested constituent. Boiling 3-20 Rev. 3 ------- point alone would not account for any non-ideal behavior of the solution. Accordingly, EPA will examine the concentrations of oil and grease, total dissolved solids, and total dissolved volatile solids. All of these characteristics affect the partial pressures of the individual organic constituents of concern as well as the solubility. Accordingly, these characteristics will affect relative volatility of a constituent and, hence, the ability of the constituent to be treated using steam stripping. The WCAPs for the steam stripper are the vapor pressures of the various constituents in the waste. The higher the vapor pressure, the more easily stripped. At 40°C, benzene has a vapor pressure of 182.7 mm Hg, aniline has a vapor pressure of 2.90 mm Hg, and phenol has a vapor pressure of 2.02 mm Hg. Nitrobenzene has a vapor pressure of 1 mm Hg at 44.4°C, and 2,4-dinitrophenol has a vapor pressure of 1 mm Hg at 49.3°C. The cyanides present are primarily solid salts, and hence have low vapor pressures or decompose upon heating. There are no known azeotropes among the constituents of these wastes, and there is no known polymerization potential upon heating these wastes. (5) Design and Operating Parameters EPA's analysis of whether a steam stripping system is well designed will focus on the degree of separation the system is designed to achieve and the controls installed to maintain the 3-21 Rev. 3 ------- proper operating conditions. The specific parameters are presented below. (1) Treated and Untreated Concentrations. In determining whether to sample a particular steam stripper as a candidate for BOAT, EPA will pay close attention to the treated design concentration of the unit to ensure that it is consistent with best demonstrated practice. This evaluation is important in that a treatment system will usually not perform its design. The various untreated waste characteristics that affect performance are important to know, because operation of the system with untreated waste concentrations in excess of initial design conditions can easily result in poor performance of the treatment unit. In evaluating the performance of a steam stripper, EPA would want data on the untreated waste characteristics to ensure that they conformed with design specifications. (2) Vapor-Liquid Equilibrium Data. The vapor liquid equilibrium data are determined in laboratory tests unless already available. The use of these data are required for several reasons. First, they are used to calculate the number of theoretical stages required to achieve the desire separation. Using the theoretical number of stages, the actual number of V stages can then be determined through the use of empirical tray efficiency data supplied by an equipment manufacturer. 3-22 Rev. 3 ------- Secondly, the vapor liquid equilibrium data are used to determine the liquid and vapor flow rates that ensure sufficient contact between the liquid and vapor streams. These rates are, in turn, used to determine the column diameter. (3) Column Temperature and Pressure. These parameters are integrally related to the vapor liquid equilibrium conditions. Column temperature design include performing a heat balance around the steam stripping unit, accounting for the heat removed in the condenser, heat input in the feed, heat input from steam injectors and heat loss from the column. Column pressure influences the boiling point of the liquid. For example, the column temperature required to achieve the desired separation can be reduced by operating the system under vacuum. During treatment, it is important to continuously monitor these parameters to ensure that the system is operated at design conditions. (4) Column Internals. Column internals are designed to accommodate the physical and chemical properties of the wastewater to be stripped. Two types of internals may be used in steam stripping: trays or packing. Tray types include bubble cap, sieve, valve and turbo-grid. Trays have several advantages • over packing. Trays are less susceptible to blockage by solids, they have a lower capital cost for large diameter columns (greater than or equal to 3 feet), and they accommodate a wider 3-23 Rev. 3 ------- range of liquid and vapor flow rates. Compared to trays, packing has the advantages of having a lower pressure drop per theoretical stage, being more resistant to corrosive materials, having a lower capital cost for small diameter column (less than 3 feet), and finally being less susceptible to foaming because of a more uniform flow distribution. 3.2.3 Carbon Adsorption Adsorption with activated carbon is an important separation method for removing organics and some other dissolved materials from liquids. It occurs when the surface of the activated carbon attracts the ions or molecules of the organic or dissolved solid to form a layer on the carbon surface and accumulate in its pores. (1) Applicability and Use of Technology Activated carbon treatment is used to remove dissolved organic pollutants from aqueous streams. To a lesser extent it also is used to remove dissolved heavy metal and other inorganic contaminants. Inorganics are usually not very adsorbable, but there are some exceptions (e.g., molybdates, gold chloride, v mercuric chloride, silver salts and iodine). The most effective metals removal occurs with metal/inorganic complexes, or metal organic complexes. 3-24 Rev. 3 ------- Activated carbon treatment is not selective in the organic contaminants it will remove. Hence, all organics will compete for system capacity, including organics that are not necessary to remove. In some systems (downflow granular activated carbon beds), suspended solids over 50 mg/1 cannot be tolerated and must be removed prior to activated carbon treatment. Activated carbon is frequently applied as a final polishing mechanism following other treatment technologies (e.g., biological treatment). These waste component separations most commonly occur in industries manufacturing organic chemicals, inorganic chemicals, dyes and pigments, insecticides, refineries, textiles, explosives, food, tobacco, leather, primary metals, fabricated metals, Pharmaceuticals, and plastics. (2) Underlying Principles of Operation Activated carbon treatment is an application of the principle of adsorption. Adsorption is the mass transfer of a molecule from a liquid or gas into a solid surface. Activated carbon is manufactured in such a way as to produce extremely porous carbon particles, whose internal surface area is very large (500 to 1400 square meters per gram of carbon). This porous structure, through chemical and physical forces, attracts and holds (adsorbs) organic molecules as well as certain 3-25 Rev. 3 ------- inorganic molecules. It is not unusual for activated carbon to adsorb from aqueous solution 0.15 grams of an organic contaminant per gram of carbon, though 0.10 gram/gram is probably a more realistic general estimate. The principal factor that affects carbon adsorption is the chemical affinity between the carbon and the organic compound. Other characteristics such as solubility, temperature, pH, type of activated carbon used and presence of other organics also influence the effectiveness of carbon adsorption. The effectiveness of adsorption generally improves with increasing contact time. Exceptions to this rule include chemical compounds that are not preferentially adsorbed onto the carbon surface. These compounds can be adsorbed from adsorption sites in favor of compounds that have a higher affinity for the carbon over a longer contact time. Once the contaminants/impurities have been removed from the waste stream onto the carbon, two options are available. The activated carbon can be (1) disposed of by approved methods (usually incineration) or (2) regenerated by thermal or chemical methods for further use. V There is a loss of performance with each regeneration step; therefore, the activity is never restored to its original level. The number of times that the carbon can be regenerated is 3-26 Rev. 3 ------- determined by the extent of physical erosion and the loss of adsorptive capacity. Isotherm tests on the regenerated carbon can be used to determine adsorptive capacity, thereby aiding in the prediction of the number of times the carbon can be regenerated. (3) Waste Characteristics Affecting Performance The waste characteristics that will affect an activated carbon system's performance are as follows: (i) type of organic contaminants, (ii) concentration of contaminants, and (iii) suspended solids, grease and oil concentration. At first, it might appear that pH and temperature would be significant factors that would affect adsorption. Polarity of some organic compounds are affected by pH, and polarity changes influence adsorption. Particularly with heavy metals, the activated carbon must have the proper pH to achieve satisfactory removal. Temperature becomes a significant factor when they become high enough to desorb contaminants from activated carbon (usually over 100°C). However, these factors are considered to be easily controlled during the actual process and, as such, are not major hindrances to efficient adsorption. 3-27 Rev. 3 ------- i. Type of Organic Contaminants All organic molecules can be adsorbed by activated carbon to some degree. Generally, adsorption will increase with molecular weight until the particle size becomes too large for carbon pore size. However, the activated carbon usually has a greater affinity for aromatic compounds than straight chain compounds. Nonpolar compounds are usually easily adsorbed, whereas polar ones are not. Halogenated organic compounds (HOCs), if aromatic (such as PCBs), are readily adsorbed. Finally, it has been demonstrated in practice that adsorption will increase with decreasing solubility. For the carbon adsorption system, the WCAPs are the molecular weights of the constituents present. The molecular weights of the major constituents in the waste are as follows: 78.12 for benzene, 123.11 for nitrobenzene, 93.13 for aniline, 94.11 for phenol, and 184.11 for 2,4-dinitrophenol. The cyanides present are thought to be a mixture of complex organic and inorganic cyanide compounds, and therefore the molecular weight cannot be determined. Other important characteristics of the waste for the carbon adsorption unit are the total organic carbon content (which is 444 mg/1) and the total suspended solids content (which is 196 mg/1). The amount of oil and grease in the waste is not known. 3-28 Rev. 3 ------- ii. Concentration of Contaminants In actual practice this process becomes ineffective at concentrations exceeding a few thousand mg/1. The carbon will adsorb concentrated contaminants so fast that carbon consumption will become excessive, and frequent disposal and/or regeneration of carbon is likely to become a greater problem than removal of the organic materials from the waste stream. For excessively concentrated waste streams, other organic compound destruction techniques would probably be more appropriated (e.g., incineration or reuse as a fuel). iii. Suspended Solids and Grease and Oil Concentration In powdered activated carbon (PAC) systems, suspended solids and grease concentrations in the wastewater stream have no effect, since they are removed from the waste along with the spent PAC. However, in nonfluidized granular activated carbon (GAC) systems (see Section 4.4 for a description of these systems), the column of GAC acts as a filter for suspended particles and greases. It will eventually become plugged or binded with solids, or coated with grease and oils, and not be able to sustain the flow of wastewater. Consequently, the more suspended solids or grease and oils in the GAC column influent, the sooner it must be backwashed, hence slowing the dissolved organic compound removal rate. 3-29 Rev. 3 ------- (4) Physical Description of the Process Specific designs will depend on the waste stream to be treated and the type of end product desired. However, a few examples will provide some idea of how these systems work. i. Systems using PAC. PAC can be easily used in exiting equipment such as tanks, filtration or settling apparatus. Since it is a fine powder, it is usually put directly into the waste stream. It needs lower contact times than GAG because it adsorbs contaminants more quickly. PAC usually has less adsorption capacity than GAC, so more is required. A few treatment systems are described below. (a) Batch system. The incoming waste stream is thoroughly stirred with the PAC, usually with some type of mechanical agitator. The stirring time (contact time) is usually 20 to 30 minutes in most cases. After adsorption equilibrium is reached, the mixture is settled and/or filtered to separate the PAC from the wastewater. This procedure can be separated to increase filtrate clarity. (b) Continuous system. In a continuous system both the waste liquid and carbon slurry enter mixing tanks simultaneously and continuously. Continuous settling and/or filtration again follow the mixing. 3-30 Rev. 3 ------- ii. Systems using GAC. In GAC systems the carbon is packed in columns and the liquid is passed through a bed of the carbon. The liquid flow can be either up or down through the vertical column. Figure 3-4 shows some common systems. Typically, the wastewater to be treated is passed downward through a stationary bed of carbon. The constituent to be removed is adsorbed most rapidly and effectively by the upper few layers of fresh carbon during the initial stages of operation. These upper layers are in contact with the wastewater at its highest concentration level. The small amounts of target constituent that escape adsorption in the first few layers of the activated carbon are removed from solution in the lower or downstream portion of the bed. Initially, none of the constituent to be removed escapes form the adsorbent. As the liquid flows down the column, the adsorption capacity is reached in the top layers, the adsorption zone starts moving down the column. As the adsorption zone moves near the end of the bed, the concentration in the effluent rapidly approaches the influent concentration. This point in the operation is referred to as breakthrough. A breakthrough curve (Figure 3-5) is the plot of the ratio of effluent to influent concentrations versus time of operation. At breakthrough the bed is exhausted and little additional removal of the constituent will occur. At this point, the carbon must be replaced or regenerated. 3-31 Rev. 3 ------- IN OUT ••"•• —:.. •.:.••.• ••-•5.; OUT DOMNFLOH IN SERIES IN OUT Ft£vfM " V* «V &."•:" IN • •••• -liSr: OUT COCURRENT IN PARALLEL COUNTERCURHENT- EXPANDED IN SERIES SOURCE- RIZZO AND SHEPHARD 1967 FIGURE 3-4 TYPICAL COLUMN CONFIGURATIONS 3-32 Rev. 3 ------- K < o UJ LU u_ LU CD O CD ID O DC 31 LU J, GC CD g o I— o _J Q_ ID I cn LU oc ID CD »—I Li_ GO O) Q. LU en UJ o oc r> o en in d I 3HI1 01 103dS3b HUN SNOI1VU1N30NOO INSnidNI 01 JO OI1VU 3-33 Rev. 3 ------- (5) Design and Operating Parameters Design Parameters The system design must account for three parameters that affect the ability of activated carbon to adsorb contaminants: i) contact time, ii) carbon particle type and size, and iii) wastewater flow rate. i. Contact time. For both PAC/GAC systems, contact time must be determined by testing individual wastes with different activated carbon samples. Once contact time is determine for adequate removal of contaminants, tank sizing is the next step and it will depend on waste flow rate. ii. Carbon particle type and size. Activated carbon is made from a variety of substances (e.g., coal, wood), ground to many different sizes, and manufactured with "customized" pore sizes. A range of surface areas and individual pore sizes will determine the carbon's adsorptive capacity. Bench testing is recommended to determine the most effective activated carbon product for a particular waste stream and desired effluent. iii. Wastewater flow rate. GAC systems are designed for upflow or downflow operation. For both types, there are practical limits to the liquid velocity. Once the velocity and 3-34 Rev. 3 ------- contact time are determined, the bed cross-section and depth are sized to meet these requirements. Operating Parameters A number of parameters must be maintained during operation to ensure that the adsorption system adheres to the design specifications. These are: (i) waste liquid concentration, (ii) suspended oils and solids, and (iii) contact time. i. Waste liquid concentration. In GAC systems, the concentration has a direct effect on the operation of an adsorption system because if the concentration is significantly higher than the design concentration, column breakthrough will occur quickly and excessive regeneration will be required. Conversely, if, during the operation of a column, the waste liquid concentration decreases significantly, previously adsorbed molecules can be desorbed from the carbon and be discharged in the effluent stream. Additionally, changes in the waste composition can cause previously adsorbed molecules to be desorbed and replaced by molecules of a different constituent if the new constituent has a higher affinity for the carbon surface. These types of situations can lead to effluent concentrations for v- a particular waste constituent that are higher than influent concentrations. Waste liquid concentration has a lesser effect on PAC systems because the PAC is removed as it is spent. 3-35 Rev. 3 ------- Desorption is not a problem. However, if the concentration increases significantly over the design concentrations, excessive quantities of PAC may be required. In any case, the effluent must be monitored for breakthrough of contaminants. ii. Suspended oils and solids. Suspended oils and solids are not usually a problem with PAC systems. However, in GAC systems, oils and suspended solids in the waste will eventually plug the column. If the concentration of solids is significant (typically greater than 200 mg/1), the waste will need to be pretreated to remove them. In any case, suspended solids and greases present in the GAC column influent will necessitate backwashing and/or column cleaning. The need for such cleaning can be detected with pressure gauges which monitor the degree of plugging. iii. Contact time. Contact time requirements vary with the type of system but must be maintained within design specifications. Typical contact times vary between 300 and 100 minutes for GAC systems, and are somewhat lower for PAC systems. For GAC systems, typical downflow rates are between 20 and 330 1/min m2 of bed area. A typical upflow rate is 610 1/min m2 of bed area, unless the bed is fluidized in which case higher V velocities are necessary. Contact time is monitored by measuring wastewater flow rate, since system volume is predetermined. 3-36 Rev. 3 ------- 3.2.4 Incineration This section addresses the commonly used incineration technologies: Liquid injection, rotary kiln, fluidized bed incineration, and fixed hearth. A discussion is provided regarding the applicability of these technologies, the underlying principles of operation, a technology description, waste characteristics that affect performance, and finally important design and operating parameters. As appropriate the subsections are divided by type of incineration unit. (1) Applicability and Use of this Technology i. Liquid Infection Liquid injection is applicable to wastes that have viscosity values sufficiently low so that the waste can be atomized in the combustion chamber. A range of literature maximum viscosity values are reported with the low being 100 SSU and the high being 10,000 SSU. It is important to note that viscosity is temperature dependent so that while liquid injection may not be applicable to a waste at ambient conditions, it may be applicable when the waste is heated. Other factors that affect the use of liquid injection are particle size and the presence of suspended solids. Both of these waste parameters can cause plugging of the burner nozzle. 3-37 Rev. 3 ------- ii. Rotary Kiln/ Fluidized Bed/ Fixed Hearth These incineration technologies are applicable to a wide range of hazardous wastes. They can be used on wastes that contain high or low total organic content, high or low filterable solids, various viscosity ranges, and a range of other waste parameters. EPA has not found these technologies to be demonstrated on wastes that are comprised essentially of metals with low organic concentrations. In addition, the Agency expects that some of the high metal content wastes may not be compatible with existing and future air emission limits without emission controls far more extensive than currently practiced. (2) Underlying Principles of Operation i. Liquid Injection The basic operating principle of this incineration technology is that incoming liquid wastes are volatilized and then additional heat is supplied to the waste to destabilize the chemical bonds. Once the chemical bonds are broken, these constituents react with oxygen to form carbon dioxide and water vapor. The energy needed to destabilize the bonds is referred to as the energy of activation. V ii. Rotary Kiln and Fixed Hearth There are two distinct principles of operation for these incineration technologies, one for each of the chambers involved. 3-38 Rev. 3 ------- In the primary chamber, energy, in the form of heat, is transferred to the waste to achieve volatilization of the various organic waste constituents. During this volatilization process some of the organic constituents will oxidize to CO and water £t vapor. In the secondary chamber, additional heat is supplied to overcome the energy requirements needed to destabilize the chemical bonds and allow the constituents to react with excess oxygen to form carbon dioxide and water vapor. The principle of operation for the secondary chamber is similar to liquid injection. iii. Fluidized Bed The principle of operation for this incinerator technology is somewhat different than for rotary kiln and fixed hearth incineration relative to the functions of the primary and secondary chambers. In fluidized bed, the purpose of the primary chamber is not only to volatilize the wastes but also to essentially combust the waste. Destruction of the waste organics can be accomplished to a better degree in the primary chamber of this technology than for rotary kiln and fixed hearth because of 1) improved heat transfer from fluidization of the waste using forced air and 2) the fact that the fluidization process provides sufficient oxygen and turbulence to convert the organics to V carbon dioxide and water vapor. The secondary chamber (referred to as the freeboard) generally does not have an afterburner; however, additional time is provided for conversion of the 3-39 Rev. 3 ------- organic constituents to carbon dioxide, water vapor, and hydrochloric acid if chlorine is present in the waste. (3) Description of Incineration Technologies i. Liquid Injection The liquid injection system is capable of incinerating a wide range of gases and liquids. The combustion system has a simple design with virtually no moving parts. A burner or nozzle atomizes the liquid waste and injects it into the combustion chamber where it burns in the presence of air or oxygen. A forced draft system supplies the combustion chamber with air to provide oxygen for combustion and turbulence for mixing. The combustion chamber is usually a cylinder lined with refractory (i.e., heat resistant) brick and can be fired horizontally, vertically upward, or vertically downward. Figure 3-6 illustrates a liquid injection incineration system. ii. Rotary Kiln A rotary kiln is a slowly rotating, refractory-lined cylinder that is mounted at a slight incline from the horizontal (see Figure 3-7). Solid wastes enter at the high end of the kiln, and liquid or gaseous wastes enter through atomizing nozzles in the kiln or afterburner section. Rotation of the kiln exposes the solids to the heat, vaporizes them, and allows them to combust by mixing with air. The rotation also causes the ash to move to the lower end of the kiln where it can be removed. 3-40 Rev. 3 ------- LJ o: O O 00 -J2 < OO O Q_0 LL) t o cr o ~ ^ M 9 ^ a: ID — 00^ I Zi i= 1 — ~ — ^* — >- [-+- 01 > ^ - z z o: O ^ 01 < P LJ Z3 Q (/) GO m z z) ^ en o m < LJ 0 ^ x 1— LJ Q ------- GAS TO AIR POLLUTION CONTROL AUXILIARY FUEL SOLID WASTE INFLUENT FEED MECHANISM AFTERBURNER COMBUSTION GASES LIQUID OR GASEOUS WASTE INJECTION ASH FIGURE 3-7 ROTARY KILN INCINERATOR 3-42 Rev. 3 ------- Rotary kiln systems usually have a secondary combustion chamber or afterburner following the kiln for further combustion of the volatilized components of solid wastes. iii. Fluidized Bed A fluidized bed incinerator consists of a column containing inert particles such as sand which is referred to as the bed. Air, driven by a blower, enters the bottom of the bed to fluidize the sand. Air passage through the bed promotes rapid and uniform mixing of the injected waste material within the fluidized bed. The fluidized bed has an extremely high heat capacity (approximately three times that of flue gas at the same temperature), thereby providing a large heat reservoir. The injected waste reaches ignition temperature quickly and transfers the heat of combustion back to the bed. Continued bed agitation by the fluidizing air allows larger particles to remain suspended in the combustion zone. (See Figure 3-8). iv. Fixed Hearth Incineration Fixed hearth incinerators, also called controlled air or starved air incinerators, are another major technology used for hazardous waste incineration. Fixed hearth incineration is a two-stage combustion process (see Figure 3-9). Waste is ram-fed » into the first stage, or primary chamber, and burned at less than stoichiometric conditions. The resultant smoke and pyrolysis products, consisting primarily of volatile hydrocarbons and 3-43 Rev. 3 ------- WASTE INJECTION FREEBOARD GAS TO AIR POLLUTION CONTROL MAKE-UP SAND AIR ASH FIGURE 3-8 FLUIDIZED BED INCINERATOR 3-44 Rev. 3 ------- cr 7 _ o cr o: i_ id < co GO 2 Z> S E^ ^ °- o o Ld 01 o LJ m ct: Ld Q O Ld l~r X < L1- Ld Ld 5 O O CO C\J CO < CE UJ O I DC UJ Q LU X u. CO 111 DC O < 3-45 Rev. 3 ------- carbon monoxide, along with the normal products of combustion, pass to the secondary chamber. Here, additional air is injected to complete the combustion. This two-stage process generally yields low stack particulate and carbon monoxide (CO) emissions. The primary chamber combustion reactions and combustion gas are maintained at low levels by the starved air conditions so that particulate entrainment and carryover are minimized. v. Air Pollution Controls Following incineration of hazardous wastes, combustion gases are generally further treated in an air pollution control system. The presence of chlorine or other halogens in the waste requires a scrubbing or absorption step to remover HCl and other halo-acids from the combustion gases. Ash in the waste is not destroyed in the combustion process. Depending on its composition, ash will either exit as bottom ash, at the discharge end of a kiln or hearth for example, or as particulate matter (fly ash) suspended in the combustion gas stream. Particulate emissions from most hazardous waste combustion systems generally have particle diameters less than one micron and require high efficiency collection devices to minimize air emissions. In addition, scrubber systems provide additional buffer against accidental releases of incompletely destroyed waste products due V to poor combustion efficiency or combustion upsets, such as flame outs. 3-46 Rev. 3 ------- (4) Waste Characteristics Affecting Performance (WCAP) i. Liquid Injection In determining whether liquid injection is likely to achieve the same level of performance on an untested waste as a previously tested waste, the Agency will compare dissociation bond energies of the constituents in the untested and tested waste. This parameter is being used as a surrogate indicator of activation energy which, as discussed previously, destabilizes molecular bonds. In theory, the bond dissociation energy would be equal to the activation energy; however, in practice this is not always the case.Other energy effects (e.g., vibrational, the formation of intermediates, and interactions between different molecular bonds) may have a significant influence on activation energy. Because of the shortcomings of bond energies in estimating activation energy, EPA analyzed other waste characteristic parameters to determine if these parameters would provide a better basis for transferring treatment standards from an untested waste to a tested waste. These parameters include heat of combustion, heat of formation, use of available kinetic data to predict activation energies, and general structural class. t> All of these were rejected for reasons provided below. 3-47 Rev. 3 ------- The heat of combustion only measures the difference in energy of the products and reactants; it does not provide information on the transition state (i.e., the energy input needed to initiate the reaction). Heat of formation is used as a predictive tool for whether reactions are likely to proceed; however, there are a significant number of hazardous constituents for which these data are not available. Use of kinetic data were rejected because these data are limited and could not be used to calculate free energy values (&G) for the wide range of hazardous constituents to be addressed by this rule. Finally, EPA decided not to use structural classes because the Agency believes that evaluation of bond dissociation energies allows for a more direct determination of whether a constituent will be destabilized. ii. Rotary Kiln/Fluidized Bed/Fixed Hearth Unlike liquid injection, these incineration technologies also generate a residual ash. Accordingly, in determining whether these technologies are likely to achieve the same level of performance on an untested waste as a previously tested waste, EPA would need to examine the waste characteristics that affect volatilization of organics from the waste, as well as, destruction of the organics, once volatilized. Relative to volatilization, EPA will examine thermal conductivity of the entire waste and boiling point of the various constituents. As with liquid injection, EPA will examine bond energies in 3-48 Rev. 3 ------- determining whether treatment standards for scrubber water residuals can be transferred from a tested waste to an untested waste. Below is a discussion of how EPA arrived at thermal conductivity and boiling point as the best method to assess volatilization of organics from the waste; the discussion relative to bond energies is the same for these technologies as for liquid injection and will not be repeated here. Thermal Conductivity Consistent with the underlying principles of incineration, a major factor with regard to whether a particular constituent will volatilize is the transfer of heat through the waste. In the case of rotary kiln, fluidized bed, and fixed hearth incineration, heat is transferred through the waste by three mechanisms: radiation, convection, and conduction. For a given incinerator, heat transferred through various wastes by radiation is more a function of the design and type of incinerator than the waste being treated. Accordingly, the type of waste treated will have a minimal impact on the amount of heat transferred by radiation. With regard to convection, EPA also believes that the type of heat transfer will generally be more a function of the type and design of incinerator than the waste itself. However, • EPA is examining particle size as a waste characteristic that may significantly impact the amount of heat transferred to a waste by convection and thus impact volatilization of the various organic 3-49 Rev. 3 ------- compounds. The final type of heat transfer, conduction, is the one that EPA believes will have the greatest impact on volatilization of organic constituents. To measure this characteristic, EPA will use thermal conductivity; an explanation of this parameter, as well as, how it can be measured is provided below. Heat flow by conduction is proportional to the temperature gradient across the material. The proportionality constant is a property of the material and referred to as the thermal conductivity. (Note: The analytical method that EPA has identified for measurement of thermal conductivity is named "Guarded, Comparative, Longitudinal Heat Flow Technique"; it is described in Appendix F.) In theory, thermal conductivity would always provide a good indication of whether a constituent in an untested waste would be treated to the same extent in the primary incinerator chamber as the same constituent in a previously tested waste. In practice, thermal conductivity has some limitations in assessing the transferability of treatment standards; however, EPA has not identified a parameter that can provide a better indication of heat transfer characteristics of a waste. Below is V a discussion of both the limitations associated with thermal conductivity, as well as other parameters considered. 3-50 Rev. 3 ------- Thermal conductivity measurements, as part of a treatability comparison for two different wastes through a single incinerator, are most meaningful when applied to wastes that are homogeneous (i.e., major constituents are essentially the same). As wastes exhibit greater degrees of non-homogeneity (e.g., significant concentration of metals in soil), then thermal conductivity becomes less accurate in predicting treatability because the measurement essentially reflects heat flow through regions having the greatest conductivity (i.e., the path of least resistance) and not heat flow through all parts of the waste. BTU value, specific heat, and ash content were also considered for predicting heat transfer characteristics. These parameters can no better account for non-homogeneity than thermal conductivity; additionally, they are not directly related to heat transfer characteristics. Therefore, these parameters do not provide a better indication of heat transfer that will occur in any specific waste. Boiling Point Once heat is transferred to a constituent within a waste, then removal of this constituent from the waste will depend on its volatility. As a surrogate of volatility, EPA is using v boiling point of the constituent. Compounds with lower boiling points have higher vapor pressures and, therefore, would be more likely to vaporize. The Agency recognizes that this parameter 3-51 Rev. 3 ------- does not take into consideration the impact of other compounds in the waste on the boiling point of a constituent in a mixture; however, the Agency is not aware of a better measure of volatility that can easily be determined. (5) Incineration Design and Operating Parameters i. Liquid Injection For a liquid injection unit, EPA's analysis of whether the unit is well designed will focus on (1) the likelihood that sufficient energy is provided to the waste to overcome the activation level for breaking molecular bonds and (2) whether sufficient oxygen is present to convert the waste constituents to carbon dioxide and water vapor. The specific design parameters that the Agency will evaluate to assess whether these conditions are met are: temperature, excess oxygen, and residence time. Below is a discussion of why EPA believes these parameters to be important, as well as a discussion of how these parameters will be monitored during operation. It is important to point out that, relative to the development of land disposed restriction standards, EPA is only concerned with these design parameters when a quench water or • scrubber water residual is generated from treatment of a particular waste. If treatment of a particular waste in a liquid injection unit would not generate a wastewater stream, then the 3-52 Rev. 3 ------- Agency, for purposes of land disposal treatment standards, would only be concerned with the waste characteristics that affect selection of the unit, not the above-mentioned design parameters. Temperature Temperature is important in that it provides an indirect measure of the energy available (i.e., BTUs/hr) to overcome the activation energy of waste constituents. As the design temperature increases, the more likely it is that the molecular bonds will be destabilized and the reaction completed. The temperature is normally controlled automatically through the use of instrumentation which senses the temperature and automatically adjusts the amount of fuel and/or waste being fed. The temperature signal transmitted to the controller can be simultaneously transmitted to a recording device, referred to as a strip chart, and thereby continuously recorded. To fully assess the operation of the unit, it is important to know not only the exact location in the incinerator that the temperature is being monitored but also the location of the design temperature. Excess Oxygen V It is important that the incinerator contain oxygen in excess of the stiochiometric amount necessary to convert the organic compounds to carbon dioxide and water vapor. If 3-53 Rev. 3 ------- insufficient oxygen is present, then destabilized waste constituents could recombine to the same or other BOAT list organic compounds and potentially cause the scrubber water to contain higher concentrations of BOAT list constituents than would be the case for a well operated unit. In practice, the amount of oxygen fed to the incinerator is controlled by continuous sampling and analysis of the stack gas. If the amount of oxygen drops below the design value, then the analyzer transmits a signal to the valve controlling the air supply and thereby increases the flow of oxygen to the afterburner. The analyzer simultaneously transmits a signal to a recording device so that the amount of excess oxygen can be continuously recorded. Again, as with temperature, it is important to know the location from which the combustion gas is being sampled. Carbon Monoxide Carbon monoxide is an important operating parameter because it provides an indication of the extent to which the waste organic constituents are being converted to CO_ and water vapor. As the carbon monoxide level increases, it indicates that greater amounts of organic waste constituents are unreacted or partially »• reacted. Increased carbon monoxide levels can result from insufficient excess oxygen, insufficient turbulence in the combustion zone, or insufficient residence time. 3-54 Rev. 3 ------- Waste Feed Rate The waste feed rate is important to monitor because it is correlated to the residence time. The residence time is associated with a specific BTU energy value of the feed and a specific volume of combustion gas generated. Prior to incineration, the BTU value of the waste is determined through the use of a laboratory device known as a bomb calorimeter. The volume of combustion gas generated from the waste to be incinerated is determined from an analysis referred to as an ultimate analysis. This analysis determines the amount of elemental constituents present which include carbon, hydrogen, sulfur, oxygen, nitrogen, and halogens. Using this analysis plus the total amount of air added, the volume of combustion gas can be calculated. Having determined both the BTU content and the expected combustion gas volume, the feed rate can be fixed at the desired residence time. Continuous monitoring of the feed rate will determine whether the unit was operated at a rate corresponding to the designed residence time. ii. Rotary Kiln For this incineration, EPA will examine both the primary and secondary chamber in evaluating the design of a particular incinerator. Relative to the primary chamber, EPA's assessment of design will focus on whether it is likely that sufficient energy will be provided to the waste in order to volatilize the waste constituents. For the secondary chamber, 3-55 Rev. 3 ------- analogous to the sole liquid injection incineration chamber, EPA will examine the same parameters discussed previously under liquid injection incineration. These parameters will not be discussed again here. The particular design parameters to be evaluated for the primary chamber are: kiln temperature, residence time, and revolutions per minute. Below is a discussion of why EPA believes these parameters to be important, as well as a discussion of how these parameters will be monitored during operation. Temperature The primary chamber temperature is important, in that it provides an indirect measure of the energy input (i.e., BTUs/hr) that is available for heating the waste. The higher the temperature is designed to be in a given kiln, the more likely it is that the constituents will volatilize. As discussed earlier under "Liquid Injection", temperature should be continuously monitored and recorded. Additionally, it is important to know the location of the temperature sensing device in the kiln. Residence Time This parameter is important in that it affects whether sufficient heat is transferred to a particular constituent in order for volatilization to occur. As the time that the waste is 3-56 Rev. 3 ------- in the kiln is increased, a greater quantity of heat is transferred to the hazardous waste constituents. The residence time will be a function of the specific configuration of the rotary kiln including the length and diameter of the kiln, the waste feed rate, and the rate of rotation. Revolutions Per Minute (RPM) This parameter provides an indication of the turbulence that occurs in the primary chamber of a rotary kiln. As the turbulence increases, the quantity of heat transferred to the waste would also be expected to increase. However, as the RPM value increases, the residence time decreases resulting in a reduction of the quantity of heat transferred to the waste. This parameter needs to be carefully evaluated because it provides a balance between turbulence and residence time. iii. Fluidized Bed As discussed previously, in the section on "Underlying Principles of Operation", the primary chamber accounts for almost all of the conversion of organic wastes to carbon dioxide, water vapor, and acid gas if halogens are present. The secondary chamber will generally provide additional residence time for thermal oxidation of the waste constituents. Relative to the V primary chamber, the parameters that the Agency will examine in assessing the effectiveness of the design are temperature, residence time, and bed pressure differential. The first two 3-57 Rev. 3 ------- were discussed under rotary kiln and will not be discussed here. The latter, bed pressure differential, is important in that it provides an indication of the amount of turbulence and, therefore, indirectly the amount of heat supplied to the waste. In general, as the pressure drop increases, both the turbulence and heat supplied increase. The pressure drop through the bed should be continuously monitored and recorded to ensure that the designed valued is achieved. iv. Fixed Hearth The design considerations for this incineration unit are similar to a rotary kiln with the exception that rate of rotation (i.e., RPMs) is not an applicable design parameter. For the primary chamber of this unit, the parameters that the Agency will examine in assessing how well the unit is designed are the same as discussed under rotary kiln; for the secondary chamber (i.e., afterburner), the design and operating parameters of concern are the same as previously discussed under "Liquid Injection". 3-58 Rev. 3 ------- 3.3 Performance Data for Wastewaters Of the three demonstrated treatment technology systems defined in Section 3.2, the Agency collected performance data for the system consisting of liquid/liquid extraction followed by steam stripping and activated carbon adsorption. This treatment system was chosen by the EPA for collecting performance data because the liquid/liquid extraction step in this three-step treatment process provides an incremental reduction in the level of organics over that obtained by either of the other two treatment processes. Performance data collected by EPA for liquid/liquid extraction followed by stream stripping and carbon adsorption are presented in Tables 3-1 to 3-5. Tables 3-1 through 3-5 present the analytical data for sample sets 1 through 5 collected during the Agency's sampling visit. The untreated K103 and K104 wastes and the combined treated steam leaving the carbon adsorption beds for each sample set were analyzed for BOAT volatile and semivolatile organic compounds, metals, inorganic compounds, and other parameters. Included in Tables 3-1 through 3-5 are the design values and actual operating ranges for the key operating parameters of the aniline liquid/liquid extractor, nitrobenzene liquid/liquid 3-59 Rev. 3 ------- TABLE 3-1 TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 1 BDAT CONSTITUENTS DETECTED Volatile Organic Compounds 4 Benzene 48 Trichloromonof luoromethane Semivolatile Organic Compounds 56 Aniline 101 2,4-Dinitrophenol 126 Nitrobenzene 142 Phenol Metals 155 Arsenic 156 Barium 159 Chromium 160 Copper 161 Lead 163 Nickel 167 Vanadium 168 Zinc Inorganics 169 Total Cyanides 170 Fluorides 171 Sulfides UNTREATED K103 ------- TABLE 3-1 (Continued) TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA3 SAMPLE SET 1 OPERATING PARAMETERS Design Value Operating Range Aniline Liquid/Liquid Extractor : Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor (°C) 7,000 - 25,000 9 - 10 40.0 14,400 - 14,500 10.3 13.0 Nitrobenzene Liquid/Liquid Extractor Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the o Extractor ( C) 27,000 - 35,000 Max. 2.4 25.0 - 65.0 21,300 - 46,000 0.2 39.0 Steam Stripper : o Top Column Temperature ( C) Pressure Drop Across the ColumnCinches of water) Feed Rate to Steam StripperCIbs/hr) Min. 95.0 Max. 90.0 Min. 20,000, Max. 90,000 95* 44.26 - 51.00 59,400 - 59,480 Activated Carbon Adsorption: Feed Rate to the System (Ibs/hr) Feed pH to the System Feed Temperature to the o System ( C) Total Organic Carbon in treated waste (mg/l) Calculated Residence time (minutes) Max. 65,300 Min. 7.0 40.0 Max. 250 Instantaneous Min. 85 61,600 - 68,600 10.6 25.0 79.3 81 - 90 a - Onsite Engineering Report for E. I. duPont de Nemours, Inc., Beaumont, Texas, Tables 4-1 through 4-3, 6-6, 6-8, and 6-14. - Not controlled. Normal operating value is given. * - Mid column substituted for top column temperature due to technical difficulties. 3-61 Rev. 3 ------- TABLE 3-2 TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 2 BOAT CONSTITUENTS DETECTED Volatile Organic Compounds 4 Benzene 48 Trichloromonof luoromethane Semi volatile Organic Compounds 56 Aniline 101 2,4-Dinitrophenol 126 Nitrobenzene 142 Phenol Metals 155 Arsenic 156 Barium 159 Chromium 160 Copper 161 Lead 163 Nickel 167 Vanadium 168 Zinc Inorganics 169 Total Cyanides 170 Fluorides 171 Sulfides UNTREATED K103 (mg/l) 73 <5 33.000 <7,500 <1,500 <1,500 <0.010 <0.001 <0.007 <0.006 <0.005 <0.011 <0.006 0.003 0.0595 <0.20 89.0 WASTE K104 320 <20 <150 <750 2,200 <150 <0.100 0.0015 0.097 <0.006 <0.100 0.055 <0.006 0.011 3.30 <0.20 <1.0* TREATED WASTE (mg/l) <0.005 0.010 <0.030 0.320 <0.030 <0.030 <0.100 0.042 0.024 <0.006 <0.050 <0.011 0.012 0.052 0.597 0.420 <1.0* * - Negative Interference Value Cont i nued 3-62 Rev. 3 ------- TABLE 3-2 (Continued) TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA3 SAMPLE SET 2 OPERATING PARAMETERS Design Value Operating Range Aniline Liquid/Liquid Extractor : Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor (°C) 7,000 - 25.000 9 - 10 40.0 15,900 - 16,000 10.3 22.0 Nitrobenzene Liquid/Liquid Extractor : Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor (°C) 27,000 - 35,000 Max. 2.4 25.0 - 65.0 9,800 - 26,000 0.2 43.0 Steam Stripper : o Top Column Temperature ( C) Pressure Drop Across the ColunrKinches of water) Feed Rate to Steam Stripper(Ibs/hr) Min. 95.0 Max. 90.0 Min. 20,000, Max. 90,000 102.2 - 103.3 42.40 - 58.00 49,000 - 60,100 Activated Carbon Adsorption: Feed Rate to the System (Ibs/hr) Feed pH to the System Feed Temperature to the o System ( C) Total Organic Carbon in treated waste (ing/ 1) Calculated Residence time (minutes) Max. 65,300 Min. 7.0 40.0 Max. 250 Instantaneous Min. 85 63,000 - 76, 4.6 28.0 73.5 73 - 88 000 a - Onsite Engineering Report for E. I. duPont de Nemours, Inc., Beaumont, Texas, Tables 4-1 through 4-3, 6-6, 6-8, and 6-14. - Not controlled. Normal operating value is given. 3-63 Rev. 3 ------- TABLE 3-3 TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 3 BOAT CONSTITUENTS DETECTED Volatile Organic Compounds 4 Benzene 48 Trichlorof luoromethane Semi volatile Organic Compounds 56 Aniline 101 2,4-Dinitrophenol 126 Nitrobenzene 142 Phenol Metals 155 Arsenic 156 Barium 159 Chromium 160 Copper 161 Lead 163 Nickel 167 Vanadium 168 Zinc Inorganics 169 Total Cyanides 170 Fluorides 171 Sulfides UNTREATED K103 (ntg/l) 65 <2.5 39,000 <15,000 <3,000 <3,000 <0.010 <0.001 <0.007 <0.006 <0.005 <0.011 <0.006 0.0099 0.0411 <0.20 74.0 WASTE K104 70 <5 <150 <750 2,300 <150 <0.010 0.011 <0.007 0.0075 <0.005 <0.011 O.006 0.031 5.70 <0.20 <1.0* TREATED WASTE (mg/l> 0.018 <0.005 4.20 <0.760 <0.150 <0.150 <0.010 0.068 0.008 <0.006 <0.005 <0.011 0.0091 0.016 0.201 0.220 <1.0* * - Negative Interference Value Cont i nued 3-64 Rev. 3 ------- TABLE 3-3 (Continued) TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA9 SAMPLE SET 3 OPERATING PARAMETERS Design Value Operating Range Aniline Liquid/Liquid Extractor : Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor (°C) 7,000 - 25,000 9 - 10 10.0 17,600 - 17,800 10.1 24.0 Nitrobenzene Liquid/Liquid Extractor Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the o Extractor ( C) 27,000 - 35,000 Max. 2.4 25.0 - 65.0 24,100 - 33,000 5.7 42.5 Steam Stripper : o Top Column Temperature ( C) Pressure Drop Across the Column(inches of water) Feed Rate to Steam Stripper(Ibs/hr) Activated Carbon Adsorption: Feed Rate to the System (Ibs/hr) Feed pH to the System Feed Temperature to the o System ( C) Total Organic Carbon in treated waste (mg/l) Calculated Residence time (minutes) Min. 95.0 Max. 90.0 Min. 20,000, Max. 90,000 Max. 65,300 Min. 7.0 40.0 Max. 250 Instantaneous Min. 85 102.6 - 103.0 46.42 - 50.33 60,200 - 60,400 57,700 - 58,140 3.1 44.0 10.8 96 - 97 a - Onsite Engineering Report for E. I. duPont de Nemours, Inc., Beaumont, Texas, Tables 4-1 through 4-3, 6-6, 6-8, and 6-14. - Not controlled. Normal operating value is given. 3-65 Rev. 3 ------- TABLE 3-4 TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 4 BOAT CONSTITUENTS DETECTED Volatile Organic Compounds 4 Benzene 48 Trichlorof luoromethane Semi volatile Organic Compounds 56 Aniline 101 2,4-Dinitrophenol 126 Nitrobenzene 142 Phenol Metals 155 Arsenic 156 Barium 159 Chromium 160 Copper 161 Lead 163 Nickel 167 Vanadium 168 Zinc Inorganics 169 Total Cyanides 170 Fluorides 171 Sulfides UNTREATED K103 (mg/D 55 <2.5 39,000 <15,000 <3.000 <3,000 0.021 <0.001 <0.007 <0.006 <0.005 <0.011 <0.006 0.018 <0.0100 <0.20 62.0 WASTE K104 11 <0.5 <300 <1,500 2,900 <300 <0.010 0.017 <0.007 <0.006 <0.005 <0.011 <0.006 0.064 3.06 <0.20 <1.0* TREATED WASTE Ong/t) 0.019 <0.005 <0.030 0.260 <0.030 <0.030 <0.500 0.076 <0.007 <0.006 <0.005 0.015 <0.006 0.033 0.156 0.220 <1.0* * - Negative Interference Value Cont i nued 3-66 Rev. 3 ------- TABLE 3-4 (Continued) TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA SAMPLE SET 4 OPERATING PARAMETERS Design Value Operating Range Aniline Liquid/Liquid Extractor : Feed Rate to the Extractor ------- TABLE 3-5 TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 5 BOAT CONSTITUENTS DETECTED Volatile Organic Compounds 4 Benzene 48 Trichlorof luoromethane Semi volatile Organic Compounds 56 Aniline 101 2,4-Dinitrophenol 126 Nitrobenzene 142 Phenol Metals 155 Arsenic 156 Barium 159 Chromium 160 Copper 161 Lead 163 Nickel 167 Vanadium 168 Zinc Inorganics 169 Total Cyanides 170 Fluorides 171 Sulfides UNTREATED WASTE K103 K104 (mg/l) 32 <2.5 53,000 <15,000 <3,000 <3,000 <0.500 <0.001 <0.007 <0.006 0.006 <0.011 <0.006 0.014 0.0384 <0.20 80.0 4.5 <0.25 <300 <1,500 3,900 <300 <0.500 0.013 0.0071 <0.006 <0.050 0.014 <0.006 0.014 4.44 <0.20 <1.0* TREATED WASTE (mg/l) 0.011 <0.005 0.960 0.230 <0.030 0.150 <0.010 0.073 0.017 <0.006 <0.100 0.030 <0.006 0.012 0.129 0.620 <1.0* Negative Interference Value Cont i nued 3-68 Rev. 3 ------- TABLE 3-5 (Continued) TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND ACTIVATED CARBON ADSORPTION - EPA COLLECTED DATA8 SAMPLE SET 5 OPERATING PARAMETERS Design Value Operating Range Aniline Liquid/Liquid Extractor : Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor ( C) 7,000 - 25,000 9 - 10 40.0 14.800 - 14,900 10.2 28.0 Nitrobenzene Liquid/Liquid Extractor Feed Rate to the Extractor (Ibs/hr) Feed pH to the Extractor Feed Temperature to the Extractor < C) 27,000 - 35,000 Max. 2.4 25.0 - 65.0 24,700 - 31,500 1.5 47.5 Steam Stripper : o Top Column Temperature ( C) Pressure Drop Across the Column(inches of water) Feed Rate to Steam Stripper(Ibs/hr) Min. 95.0 Max. 90.0 Min. 20,000, Max. 90,000 102.6 - 102.7 44.80 - 51.80 57,590 - 57,660 Activated Carbon Adsorption: Feed Rate to the System (Ibs/hr) Feed pH to the System Feed Temperature to the 0 System ( C) Total Organic Carbon in treated waste (mg/l) Calculated Residence time (minutes) Max. 65,300 Min. 7.0 40.0 Max. 250 Instantaneous Min. 85 52,200 - 61,500 3.5 33.5 7.0 91 - 107 a - Onsite Engineering Report for E. I. duPont de Nemours, Inc., Beaumont, Texas, Tables 4-1 through 4-3, 6-6, 6-8, and 6-14. - Not controlled. Normal operating value is given. 3-69 Rev. 3 ------- extractor, steam stripper, and activated carbon adsorption beds for each sample set collected. 3.4 Other Applicable Treatment Technologies The Agency does not believe that other technologies are applicable for treatment of K103 and K104 wastewaters because of various physical and chemical characteristics of the wastewaters. For a detailed description of the physical and chemical characteristics affecting treatment selection, see BOAT Background Document for the First Third Wastes, Volume 1, Section 2. Liquid/liquid extraction followed by steam stripping and activated carbon adsorption is judged to be available to treat K103 and K104 wastewaters, and incineration is judged to be available to treat K103 and K104 nonwastewaters. The Agency believes these technologies to be available because (1) the Agency does not have information showing that this technology poses a greater total risk to human health and the environment that land disposal; (2) this technology is commercially available; and (3) this technology provides a substantial reduction in the levels of BOAT constituents present in waste K103 and K104. 3-70 Rev. 3 ------- 4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TREATMENT TECHNOLOGY FOR K103 AND K104 4.1 Introduction The previous section described applicable treatment technologies for waste codes K103 and K104, and the available performance data for these technologies. This section describes how the performance data collected by the Agency was evaluated to determine which treatment technology system should be considered BOAT for waste codes K103 and K104. Several treatment trains are considered in this section as BOAT for wastewaters. They consist of: o liquid/liquid extraction, o liquid/liquid extraction followed by steam stripping, o liquid/liquid extraction followed by steam stripping and activated carbon adsorption. The use of activated carbon adsorption for treatment of K103 and K104 wastewaters generates a nonwastewater, spent carbon. The treatment considered in this section as BOAT for the nonwastewaters is rotary kiln incineration. The topics covered in this section include descriptions of V the data screening process employed for selecting BOAT, the methods used to ensure accuracy of the analytical data, and the 4-1 Rev. 3 ------- analysis of variance (ANOVA) tests performed in identifying the best technology for the treatment of K103 and K104 wastes. As discussed in Section 3, the Agency collected performance data for the treatment of waste codes K103 and K104 from one treatment technology system: liquid/liquid extraction followed by steam stripping and activated carbon adsorption. No additional performance data were available for the treatment of K103 and K104 wastes. However, the Agency is using and comparing data taken from various components of the treatment train to determine BDAT. Performance data were not available for the treatment of K103 and K104 nonwastewaters. In general, performance data are screened according to the following three conditions: o proper design and operation of the treatment system; o the existence of quality assurance/quality control measures in the data analysis; and o the use of proper analytical tests in assessing treatment performance. Sets of performance data which do not meet these three conditions are not considered in the selection of BDAT. In addition, if performance data indicate that the treatment system was not well- designed and well-operated at the time of testing, these data would also not be used. 4-2 Rev. 3 ------- The remaining performance data are then corrected to account for incomplete recovery of certain constituents during the analyses. Finally, in cases where the Agency has adequate performance data for treatment of the waste by more than one technology, an analysis of variance (ANOVA) test is used to select the best treatment technology. 4.2 Data Screening In the selection of BOAT for treatment of K103 and K104 wastewaters, the only performance data available were those collected during the Agency's sampling visit. Five data sets were collected by the Agency for treatment of the wastewaters by liquid/liquid extraction followed by steam stripping and carbon adsorption. These data were evaluated to determine whether any of the data represented poor design or operation of the system. One of the data sets (Sample Set #3) was deleted due to poor operation of the carbon adsorption unit during the time data were being collected. This was indicated by a higher than normal system temperature and a relatively high aniline concentration in the treated waste. The four remaining data sets were used for the development of treatment standards for K103 and K104 wastewaters. These data sets are sample sets 1, 2, 4 and 5. k- Toxic Characteristic Leaching Procedure (TCLP) data were not used in setting treatment standards for waste codes K103 and K104 4-3 Rev. 3 ------- because metals were not identified as one of the classes of BOAT list constituents for regulation (see Section 5 for further details). For a discussion on the use of TCLP data in setting treatment standards, refer to Section 1 of this background document. In instances where a selected constituent was not detected in the treated waste, the treated value for that constituent was assumed to be the practical quantification level. This was the case for the following constituents: (1) benzene in Sample Set #2; (2) aniline in Sample Sets #1, #2, and #4; (3) nitrobenzene in Sample Sets #1, #2, #4, and #5; (4) phenol in Sample Sets #1, #2, and #4. Analytical values for the treated waste are presented in Table 4-1. 4.3. Data Accuracy After data were eliminated from consideration for analysis of BOAT based on the screening tests, the Agency adjusted the remaining data using analytical recovery values in order to take into account analytical interferences and incomplete recoveries associated with the chemical makeup of the sample. The Agency developed the recovery data (also referred to as accuracy data), »- by first analyzing a waste for a given constituent and then by adding a known amount of the same constituent (i.e., spike) to the waste material. The total amount recovered after spiking, 4-4 Rev. 3 ------- TABLE 4-1 Treatment Data Used for Regulation of K103 and K104 Wastewaters ANALYTICAL CONCENTRATIONS (1) BOAT List Constituent Benzene Ani line 2,4-Dinitrophenol Nitrobenzene Phenol Total Cyanides Sample Set 1 (total) (mg/l) 0.042 <0.030 0.380 <0.030 <0.030 0.565 Sample Set 2 (total) (mg/l) <0.005 <0.030 0.320 <0.030 <0.030 0.597 Sample Set 4 (total) (mg/l) 0.019 <0.030 0.260 <0.030 <0.030 0.156 Sample Set 5 (total) (mg/l) 0.011 0.960 0.230 <0.030 0.150 0.129 ACCURACY-CORRECTED CONCENTRATIONS (2) BOAT List Const i tuent Benzene Ani line 2,4-Dinitrophenol Nitrobenzene Phenol Total Cyanides Sample Set 1 (total) (mg/l) 0.055 0.033 0.475 0.026 0.143 0.785 Sample Set 2 (total) (mg/l) 0.007 0.033 0.400 0.026 0.143 0.830 Sample Set 4 (total) (mg/l) 0.025 0.033 0.325 0.026 0.143 0.217 Sample Set 5 (total) (mg/l) 0.015 1.056 0.288 0.026 0.714 0.179 1. Onsite Engineering Report for E.I. du Pont de Nemours, Inc., Beaumont, Texas, Tables 6-14. 2. Calculations shown in Appendix D of this Background Document. 4-5 Rev. 3 ------- minus the initial concentration in the sample, divided by the amount added, is the recovery value. At least two recovery values were calculated for spiked constituents, and the analytical data were adjusted for accuracy using the lowest recovery value for each constituent. This was accomplished by calculating an accuracy factor from the percent recoveries for each selected constituent. The reciprocal of the lower of the two recovery values divided by 100, yields the accuracy factor. The corrected concentration for each sample set is obtained by multiplying the accuracy factor by the raw data value. The actual recovery values and accuracy factors for the selected constituents are presented in Appendix E. The accuracy factors calculated for the selected constituents varied from a high value of 4.76 for phenol to a low value of 0.87 for nitrobenzene. The corrected concentration values for the selected constituents are shown for the four data sets in Table 6-1. These corrected concentrations values were obtained by multiplying the accuracy factors (Appendix E) by the concentration values for the selected constituents in the treated waste. An arithmetic average value, representing the treated waste concentration, was calculated for each selected constituent from the four corrected values. These averages are presented in Table 6-1. These adjusted values for the treatment technology 4-6 Rev. 3 ------- system consisting of liquid/liquid extraction followed by steam stripping and activated carbon adsorption were then used to determine BDAT for waste codes K103 and K104. 4.4 Analysis of Variance In cases where the Agency has adequate performance data on treatment of the same or similar wastes using more than one technology, an analysis of variance (ANOVA) test is performed to determine if one of the technologies provides significantly the best treatment than the others. In cases where a particular treatment technology is shown to provide better treatment, the treatment standards will be used on this best technology. The procedure followed for the analysis of variance (ANOVA) test is described in Appendix A. In order to determine BDAT for waste codes K103 and K104, three combinations of demonstrated technologies, for which adequate performance data were available, were considered for the treatment of these wastes: o Liquid/liquid extraction, o Liquid/liquid extraction followed by steam stripping, and o Liquid/liquid extraction followed by steam stripping and activated carbon adsorption. 4-7 Rev. 3 ------- The corrected data for sample sets 1, 2, 4, and 5 were used to perform analysis of variance (ANOVA) tests to compare these three technology combinations. The three combinations of treatment technologies were compared based on the concentration of primary waste constituents (benzene, aniline, nitrobenzene, phenol, 2,4-dinitrophenol, and total cyanides) in the treated waste. The rationale for selecting these constituents for the ANOVA comparison is presented in Section 6. The statistical results of the ANOVA test for liquid/liquid extraction followed by steam stripping versus liquid/liquid extraction indicate the following: 1) Liquid/liquid extraction followed by steam stripping provides significantly better treatment for benzene and nitrobenzene in waste codes K103 and K104 than liquid/liquid extraction alone. 2) Liquid/liquid extraction followed by steam stripping provides equivalent treatment for total cyanides in waste codes K103 and K104 compared to liquid/liquid extraction alone. »• 3) Insufficient data exist to compare the treatment for phenol, aniline, and 2,4-dinitrophenol achieved by 4-8 Rev. 3 ------- liquid/liquid extraction alone with that achieved by liquid/liquid extraction followed by steam stripping. The statistical results of the ANOVA test of liquid/liquid extraction followed by steam stripping and activated carbon adsorption versus liquid/liquid extraction followed by steam stripping indicate the following: 1) Liquid/liquid extraction followed by steam stripping and activated carbon adsorption provides significantly better treatment for aniline, 2,4-dinitrophenol, phenol and total cyanides in waste codes K103 and K104 than liquid/liquid extraction followed by steam stripping. 2) Liquid/liquid extraction followed by steam stripping and activated carbon adsorption provides equivalent treatment for benzene in waste codes K103 and K104 compared to liquid/liquid extraction followed by steam stripping. 3) Insufficient data exist to compare the treatment for nitrobenzene achieved by liquid/liquid extraction followed by steam stripping with that achieved by liquid/liquid extraction followed by steam stripping and activated carbon adsorption. 4-9 Rev. 3 ------- The three-step treatment technology system consisting of liquid/liquid extraction followed by steam stripping and activated carbon adsorption provides significantly better or equivalent treatment overall for the primary constituents present in waste codes K103 and K104 when compared either liquid/liquid extraction alone or liquid/liquid extraction followed by steam stripping. Therefore, the Agency has chosen this three-step treatment system to be BOAT for waste codes K103 and K104. 4-10 Rev. 3 ------- 5. SELECTION OF REGULATED CONSTITUENTS In the previous section, the best demonstrated available technology (BOAT) for treating the wastewater forms of waste codes K103 and K104 was determined to be liquid/liquid extraction followed by steam stripping and activated carbon adsorption. The two nonwastewater forms of K103 and K104 are as follows: spent carbon from the activated carbon adsorber and the solvent- extract stream from the nitrobenzene liquid/liquid extractor. Based on analysis of the influent and effluent streams (see Tables 6-13 and 6-14 in the OER for K103 and K104) from the activated carbon adsorber, the Agency expects the spent carbon to contain the following constituents: benzene, aniline, 2,4- dinitrophenol, nitrobenzene, phenol, and cyanides. Rotary kiln incineration has been demonstrated on wastes that are similar to the spent carbon from the activated carbon adsorber. Therefore, the Agency believes that rotary kiln incineration is BOAT for the spent carbon from the activated carbon adsorber. Rotary kiln incineration has also been demonstrated on wastes that are similar to the solvent-extract stream from the nitrobenzene liquid/liquid extractor. Therefore, the Agency believes that rotary kiln incineration is BOAT for the solvent- extract from the nitrobenzene liquid/liquid extractor. In this section, the necessary constituents are identified for assuring 5-1 Rev. 3 ------- the most effective treatment of the wastes. This is done by following a three-step procedure: o identifying the BOAT list constituents found in both the untreated and treated waste; o determining the classes of BDAT list constituents present, and o selecting the regulated constituents. As discussed in Section 1, the Agency has developed a list of hazardous constituents (Table 1-1) from which the constituents to be regulated are selected. The list is a "growing list" that does not preclude the addition of new constituents as additional key parameters are identified. The list is divided into the following categories: volatile organics, semivolatile organics, metals, inorganics, organochlorine pesticides, phenoxyacetic acid herbicides, organophosphorous pesticides, PCBs, and dioxins and furans. The constituents in each category have similar chemical properties and are expected to behave similarly during treatment, with the exception of the inorganics. 5.1 Identification of BDAT List Constituents in the Untreated and Treated Waste Using EPA-collected data, the Agency identified those constituents that were detected in the untreated and treated V waste. The BDAT list of constituents (see Table 1-1, Section 1.0) provided the target list of constituents. EPA collected five sets of data at one facility (see the Onsite Engineering 5-2 Rev. 3 ------- Report for K103 and K104 for more details) to evaluate the treatment of the wastewater forms of waste codes K103 and K104 by liquid/liquid extraction followed by steam stripping and activated carbon adsorption. One of the five data sets (data set #3) was eliminated because the activated carbon adsorber was not well-operated during the sampling interval. Poor operation of the activated carbon adsorption system was indicated by a higher than normal system temperature and a relatively high aniline concentration in the treated waste. The remaining four data sets were used to identify the constituents detected in the untreated and treated waste. The detection limits for the BOAT list of constituents are presented in Appendix C. Table 5-1 presents the BOAT list as discussed in Section 1. It indicates which of the BOAT list constituents were analyzed in the untreated and treated waste. This table also gives the concentrations of those BOAT list constituents which were detected. As shown in Table 5-1, the following constituents were detected in the untreated waste K103: benzene, aniline, arsenic, lead, zinc, total cyanides, and sulfides. The following constituents were detected in the untreated waste K104: benzene, nitrobenzene, barium, chromium, copper, nickel, zinc, total cyanides, and sulfides. The following constituents were detected V in the treated waste (K103 and K104): benzene, aniline, 2,4-dinitrophenol, trichloromonofluoromethane, phenol, barium, chromium, nickel, vanadium, zinc, total cyanides, and fluorides. 5-3 Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste Parameter Untreated K103 (mg/l) Untreated K104 (mg/l) Treated K103/K104 (mg/l) Volatiles 222 1 2 3 4 5 6 223 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 224 225 226 30 227 31 214 32 Acetone Acetonitrile Acrolein Acrylonitrile Benzene Bromodichloromethane Bromomethane n-Butyl alcohol Carbon Tetrachloride Carbon disulfide Chlorobenzene 2-Chloro-1,3-butadiene Ch 1 orodi bromomethane Chloroethane 2-Chloroethyl vinyl ether Chloroform Chloromethane 3-Chloropropene 1,2-Dibromo-3-chloropropane 1 ,2-Dibromoethane Di bromomethane trans- 1,4-Dichloro-2-butene D i ch 1 orodi f I uoromethane 1, 1-Dichloroethene 1,2-Di Chloroethane 1, 1-Dichloroethylene trans- 1,2-Dichloroethene 1 , 2 - D i ch I oropropane trans- 1 ,3-D ich loropropene cis-1,3-Dichloropropene 1,4-Dioxane 2-Ethoxyethanol Ethyl acetate Ethyl benzene Ethyl cyanide Ethyl ether Ethyl methacrylate Ethylene oxide lodomethane ND ND ND NO 32 - 81 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 4.5 - 320 ND ND ND ND ND NO NO ND NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.011 - 0.042 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND - Not detected Continued 5-4 Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Untreated Untreated Parameter K103 K104 (mg/1) (mg/O Treated K103/K104 (mg/l) Volatiles (continued) 33 228 34 229 35 37 38 230 39 40 41 42 43 44 45 46 47 48 49 231 50 215 216 217 Isobutyl alcohol Hethanol Methyl ethyl ketone Methyl isobutyl ketone Methyl methacrylate Methylacryloni tri le Methylene chloride 2-Nitropropane Pyridine 1, 1,1,2-Tetrachloroethane 1,1.2,2-Tetrachloroethane Tetrachloroethene Toluene T r i bromomethane 1,1, 1 -Trichloroethane 1,1,2-Trichloroethane Trichloroethene Trichloromonof lurexnethane 1 ,2,3-Trichloropropane 1, 1,2-Trichloro- 1,2,2- tri fluoroethane Vinyl chloride 1,2-Xylene 1,3-Xylene 1,4-Xylene NO ND NO NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.007 - 0.010 ND ND ND ND ND NO Semivolatiles 51 52 53 54 55 56 57 58 59 218 60 61 62 Acenaphthalene Acenaphthene Acetophenone 2-Acetylaminof luorene 4-Aminobiphenyl Aniline 33000 Anthracene Arami te Benz ( a ) anth racene Benzal chloride Benzenethiol Benz i dine Benzo(a)pyrene ND ND ND ND ND - 53000 ND ND ND ND NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.96 ND ND ND ND ND ND ND ND - Not detected - Indicates that only one sample contained this constituent at detectable levels. 5-5 Continued Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Parameter Untreated K103 (mg/l) Untreated K104 (mg/l) Treated K103/K104 (mg/l) Semivolatiles (continued) 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 232 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 BenzoC b) f I uoranthene Benzo(ghi )perylene Benzo( k ) f I uoranthene p-Benzoquinone Bis(2-chloroethoxy)ethane Bis(2-chloroethyl)ether Bis(2-chloroisopropy)ether Bis(2-ethylhexy)phthalate 4-Bromophenyl phenyt ether Butyl benzyl phthlate 2-sec-Butyl-4,6-dinitrophenol p-Chloroaniline Chlorobenzi late p-Chloro-m-cresol 2-Chloronaphthalene 2-Chlorophenol 3-Chloropropionitrile Chrysene ortho-Cresol para-Cresol Cyclohexanone Dibenz(a,h)anthracene D i benzo(a, e)pyrene Dibenzo(a,i)pyrene m- D i ch I orobenzene o-Dichlorobenzene p-D i ch I orobenzene 3,3'-Dichlorobenzidine 2,4-Dichlorophenol 2,6-Dichlorophenol Di ethyl phthalate 3,3'-Dimethyoxlbenzidine p-Dimethylaminoazobenzene 3,3'-Dimethylbenzidine 2,4-Dimethylphenol Dimethyl phthalate Di-n-butyl phthalate 1 ,4-Dini trobenzene 4,6-Dinitro-o-cresol 2,4-Dinitrophenol ND NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.23 - 0.38 ND - Not detected 5-6 Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Parameter Untreated K103 (mg/l) Untreated K104 (mg/l) Treated K103/K104 (mg/l) Semivolatiles (cont.) 102 103 104 105 106 219 107 108 109 110 111 112 113 114 115 116 117 118 119 120 36 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 2,4-Dinitrotoluene 2,6-Dinitrotoluene Di-n-octyl phthalate Di-n-propylnitrosamine Diphenylamine Diphenylni trosamine 1,2-Diphenylhydrazine Fluoranthene Fluorene Hexach lorobenzene Hexachlorobutadiene Hexach I orocyc I opentadi ene Hexach loroethane Hexach loroph ene Hexach I oropropene Indeno(1,2,3-cd)pyrene Isosafrole Methapyrilene 3-Hethycholanthrene 4,4'-Hethylenebis(2-chloroani line) Methyl methanesulfonate Napthalene 1,4-Naphthoquinone 1-Napthylamine 2-Napthylamine p-Nitroani line Nitrobenzene 4-Nitrophenol N-Nitrosodi-n-butylamine N-Ni trosodiethylamine N-Nitrosodimethylamine N -N i trosomethy I ethy 1 ami ne N-Nitrosomorpholine N-Nitrosopiperidine n-Nitrosopyrrol idine 5-Nitro-o-toluidine Pentach I orobenzene Pentach loroethane Pentach I oron i t robenzene NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 2200 - 3900 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND - Not detected 5-7 Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Parameter Semivolatiles (cont.) 139 Pentachlorophenol 140 Phenacetin 141 Phenanthrene 142 Phenol 220 Phthalic anhydride 143 2-Picoline 144 Pronamide 145 Pyrene 146 Resorcinol 147 Safrole 148 1,2,4,5-Tetrachlorobenzene 149 2,3,4, 6-Tetrachlorophenol 150 1,2,4-Trichlorobenzene 151 2,4,5-Trichlorophenol 152 2,4.6-Trichlorophenol 153 Tris(2,3-dibromopropyl)phosphate Hetals 154 Antimony 155 Arsenic 156 Barium 157 Beryllium 158 Cadmium 159 Chromium 221 Chromium (hexavalent) 160 Copper 161 Lead 162 Mercury 163 Nickel 164 Selenium 165 Si Iver 166 Thallium 167 Vanadium 168 Zinc Inorganics 169 Cyanide 170 Fluoride 171 Sulfide Untreated £103 (mg/l) NO ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.021 ND ND ND ND ND ND 0.006 ND ND ND ND ND ND 0.003 - 0.021 0.038 - 0.075 ND 62.0 - 89.0 Untreated K104 (mg/l) ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.0015 - 0.017 ND ND 0.007 - 0.432 ND 0.012 ND ND 0.014 - 0.238 ND ND ND ND 0.011 - 0.079 3.06 - 6.28 ND ND Treated K103/K104 (mg/l) ND ND ND 0.15 ND ND ND ND ND ND ND ND ND ND ND ND ND ND 0.032 - 0.076 ND ND 0.0097 - 0.024 ND ND ND ND 0.015 - 0.030 ND ND ND 0.012 - 0.014 0.012 - 0.058 0.129 - 0.597 0.220 - 0.620 ND ** - Indicates that only one sample contained this constituent at detectable levels. 5-8 Continued Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Parameter Organochlorine Pesticides 172 Aldrin 173 alpha-BHC 174 beta-BHC 175 delta- BHC 176 gamma -BHC 177 Chlordane 178 ODD 179 DDE 180 DDT 181 Dieldrin 182 Endosulfan I 183 Endosulfan II 184 Endrin 185 Endrin aldehyde 186 Heptachlor 187 Heptachlor epoxide 188 Isodrin 189 Kepone 190 Hehoxychlor 191 Toxaphene Phenoxyacetic Acid Herbicides 192 2,4-Dichlorophenoxyacetic acid 193 Silvex 194 2,4, 5-T Organophosphorous Insecticides 195 Disulfoton 196 Famphur 197 Methyl parathion 198 Paration 199 Phorate PCBs 200 Aroclor 1016 201 Aroclor 1221 202 Aroclor 1232 Untreated K103 (mg/l) NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA ND ND ND Untreated K104 (mg/l) NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA ND ND ND Treated K103/K104 (mg/l) NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA ND ND ND ND - Not detected NA - Not analyzed 5-9 Rev. 3 ------- TABLE 5-1 BOAT List Constituents in Untreated and Treated Waste (Continued) Parameter PCBs (continued) 203 Aroclor 1242 204 Aroclor 1248 205 Aroclor 1254 206 Aroclor 1260 Pi ox ins and Furans 207 Hexachlorodibenzo-p-dioxins 208 Hexachlorodibenzofuran 209 Pentachlorodibenzo-p-dioxins 210 Pentachlorodibenzofuran 211 Tetrachlorodibenzo-p-dioxins 212 Tetrachlorodibenzofuran 213 2,3,7,8-Tetrachlorodibenzo-p-dioxin Untreated K103 (mg/l) ND NO NO ND ND ND ND ND ND ND ND Untreated K104 (mg/D ND ND ND ND ND ND ND ND ND MD ND Treated K103/K104 (mg/l) ND ND ND ND ND ND ND ND ND ND ND ND - Not detected 5-10 Rev. 3 ------- Since the waste codes K103 and K104 are mixed before the steam stripping step, the analytical data for the treated waste are the same for both waste codes. The untreated and treated waste samples were not analyzed for other classes of BOAT organics (organochlorine pesticides, phenoxyacetic acid herbicides, and organophosphorus pesticides) because there is no in-process source of these constituents and because of the extreme unlikelihood of finding these constituents at treatable levels in the waste. 5.2 Determination of Classes of Constituents The BOAT list constituents in waste codes K103 and K104 belong to the following four classes: volatiles, semivolatiles, metals, and inorganics (See Table 5-1). Two volatile constituents, benzene and trichloromonofluoromethane, were detected. Four semivolatile constituents, aniline, 2,4-dinitrophenol, nitrobenzene, and phenol were also detected. Six metal constituents were also detected: arsenic, chromium, lead, nickel, vanadium, and zinc. The inorganic pollutants detected were cyanide, fluoride, and sulfide. V- The metal constituents were present in untreatable concentrations in the untreated waste codes K103 and K104. None of the metals in either untreated K103 or untreated K104 were 5-11 Rev. 3 ------- detected at a concentration level higher than 1 mg/1. Also, by comparing the concentration of metals in the untreated and treated waste for both waste codes K103 and K104, the Agency concluded that metals were not substantially treated. For a discussion of how the Agency decides when treatment is substantial, see Section 1 of this background document. The BOAT metal constituents in K103 and K104 were not present at treatable levels in the waste. Therefore, metals were eliminated as a class of BDAT list constituents to be regulated in waste codes K103 and K104. However, the remaining three classes of pollutants, namely, volatiles, semivolatiles, and inorganics, were generally present at treatable concentration levels in the untreated wastes and were judged to be substantially treated when the untreated and treated constituent data were compared for both waste codes. 5.3 Selecting the Regulated Constituents The Agency evaluated the analytical data for each constituent to determine if the constituent should be selected for regulation. In general, the Agency was guided by the criteria for selecting regulated constituents as described in Section 1 of this background document. 5-12 Rev. 3 ------- The rationale for selecting the regulated constituents from the four classes of constituents is presented below. Volatiles Benzene was present in significant concentrations in both the untreated K103 and untreated K104 streams. Benzene was selected as a regulated constituent for waste codes K103 and K104 because it was substantially treated in both waste codes. The benzene concentration in untreated K103 and untreated K104 was reduced by the treatment system to below treatable levels. Trichloromonofluoromethane was not detected in either untreated K103 or untreated K104, but was detected in the treated waste. Although this compound was reported as not detected in the untreated waste, the Agency has judged that it was present, but was masked due to high concentrations of aniline and nitrobenzene. The Agency believes that effective treatment of benzene will effectively treat trichloromonofluoromethane as well. Trichloromonofluoromethane is less soluble in water than benzene, and is soluble in nitrobenzene. This indicates that trichloromonofluoromethane will also be effectively treated by the solvent extraction step of the treatment system. v Trichloromonofluoromethane has a higher vapor pressure than benzene at 40°C, which indicates that trichloromonofluoromethane will be effectively treated by the steam stripping step of the 5-13 Rev. 3 ------- treatment system. As a result, trichloromonofluoromethane was not selected as a regulated constituent for either waste code K103 or waste code K104, because treatment for benzene will also treat trichloromonofluoromethane. Semivolatiles Aniline was detected in untreated K103 at high concentration levels. Aniline was reported as not detected in untreated K104 but it was found in the treated waste at low concentration levels. Based on data analysis, the concentration of aniline in the untreated K103 waste was substantially reduced (to be below treatable levels) by the treatment system. The Agency assumes aniline was not detected in untreated K104 because the Practical Quantification Levels were high due to matrix interferences. The Agency believes that aniline was present in untreated K104 and that it was effectively treated by the treatment system. As a result, aniline was selected as a regulated constituent for both waste codes K103 and K104. The BOAT list constituent 2,4-dinitrophenol was not detected in either untreated K103 or untreated K104. It was, however, detected in the treated waste. The Agency assumes that V 2,4-dinitrophenol was not detected in both untreated K103 and untreated K104 because the Practical Quantification Levels were high (see Appendix C) due to matrix interferences. The Agency 5-14 Rev. 3 ------- believes that 2,4-dinitrophenol was present in both untreated K103 and untreated K104 and that it was effectively treated by the treatment system. As a result, 2,4-dinitrophenol was selected as a regulated constituent for both waste codes K103 and K104. Nitrobenzene was not detected in untreated K103. It was detected in untreated K104, and it was not detected in the treated waste. The concentration of nitrobenzene in untreated K104 was substantially reduced by the treatment system. The Agency assumes that nitrobenzene was not detected in untreated K103 because the Practical Quantification Levels were high (see Appendix C) due to matrix interferences. The Agency believes that nitrobenzene was present in untreated K103 and that it was effectively treated by the treatment system. As a result, nitrobenzene was selected as a regulated constituent for both waste codes K103 and K104. Phenol was not detected in either untreated K103 or untreated K104. It was detected, however, in the treated waste. The Agency assumes that phenol was not detected in both untreated K103 and untreated K104 because the Practical Quantification Levels were high (see Appendix C) due to matrix interferences. V The Agency believes that phenol was present in both untreated K103 and untreated K104 and that it was effectively treated by 5-15 Rev. 3 ------- the treatment system. As a result, phenol was selected as a regulated constituent for both waste codes K103 and K104. Inorganics Cyanide was detected in untreated K103 and untreated K104, and also in the treated waste. Because the concentration of cyanide in untreated K103 increased when the waste was treated, the Agency concluded that cyanide in untreated K103 was not effectively treated. This apparent increase in cyanide concentration for waste code K103 was thought to be due to the mixing with waste code K104. The cyanide concentration was higher in untreated K104 than in untreated K103. The concentration of cyanide in untreated K104 was substantially reduced by the treatment system. Therefore, the Agency believes that cyanide in untreated K104 was effectively treated by the treatment system. As a result, the Agency selected cyanide as a regulated constituent for K104 but not for K103. Fluoride was not detected in either untreated K103 or untreated K104. It was, however, detected in the treated waste. The Agency has judged that fluoride was present in both untreated K103 and untreated K104 at concentration levels below the • Practical Quantification Level for the untreated waste matrix and that it was not effectively treated by the treatment system. As 5-16 Rev. 3 ------- a result, fluoride was not selected as a regulated constituent for either waste code K103 or waste code K104. Sulfide was detected in untreated K103, but was not detected in either untreated K104 or in the treated waste. The Agency recognizes that the sulfide concentration was diminished in the treated waste, but considers this an incidental treatment since the treatment technology tested is not demonstrated for the treatment of sulfides. As a result, sulfide was not selected as a regulated constituent for either waste code K103 or waste code K104. The regulated constituents for K103 are as follows: o benzene o aniline o 2,4-dinitrophenol o nitrobenzene o phenol The regulated constituents for K104 are as follows: o benzene o aniline o 2,4-dinitrophenol o nitrobenzene o phenol o total cyanides For the nonwastewater forms of K103 and K104, the same BDAT list constituents were chosen for regulation as shown above for wastewaters. This was done because the Agency did not have any data available for determining the concentration of BDAT list constituents in the nonwastewaters. 5-17 Rev. 3 ------- 6. CALCULATION OF BOAT TREATMENT STANDARDS In this section, the actual treatment standards for waste codes K103 and K104 are presented. These standards were calculated based on the performance of the demonstrated treatment system which was determined by the Agency to be the best for treating both waste codes. In Section 4, BOAT for the wastewater forms of waste codes K103 and K104 was determined to be liquid/liquid extraction followed by steam stripping and activated carbon adsorption. BOAT for the nonwastewater forms of K103 and K104 was determined to be incineration. The previous section identified the constituents to be regulated for the wastewater and nonwastewater forms of K103 and K104 wastes. As discussed in Section 1, the Agency calculated the BOAT treatment standards for waste codes K103 and K104 by following a four-step procedure: (1) editing the data; (2) correcting the remaining data for analytical interference; (3) calculating adjustment factors (variability factors) to account for process variability; and (4) calculating the actual treatment standards using variability factors and average treatment values. The four steps in this procedure are discussed in detail in Sections 6.1 through 6.4. 6-1 Rev. 3 ------- 6.1 Editing the Data Five sets of treatment data for waste codes K103 and K104 were collected by the Agency at one facility which operated a treatment system consisting of liquid/liquid extraction followed by steam stripping and activated carbon adsorption. The Agency evaluated the five data sets to determine if the treatment system was well operated at the time of the sampling visit. The Agency eliminated one data set, sample set #3, because the treatment system was not well operated when the samples were collected (as discussed in Section 5). For further details on the five data sets, see the Onsite Engineering Report for K103 and K104. The remaining four data sets were used to calculate treatment standards. Toxic Characteristic Leaching Procedure (TCLP) data were not used in setting treatment standards for waste codes K103 and K104 because metals were not one of the classes of BOAT list constituents identified for regulation (see Section 5 for further details). For a discussion on the use of TCLP data in setting treatment standards, refer to Section 1 of this background document. V In instances where a selected constituent was not detected in the treated waste, the treated value for that constituent was assumed to be the Practical Quantification Level. This was the 6-2 Rev. 3 ------- case for the following constituents: (1) benzene in sample set #2; (2) aniline in sample sets #1, #2, and #4; (3) nitrobenzene in sample sets #1, #2, #4, and #5; (4) phenol in sample sets #1, #2, and #4. Analytical values for the treated waste are presented in Section 3, Tables 3-1 through 3-5 of this report. 6.2 Correcting the Remaining Data Data values for the constituents selected for regulation were taken from the four data sets (sample sets I, 2, 4 and 5). These values were corrected in order to take into account analytical interferences associated with the chemical make-up of the treated sample. This was accomplished by calculating an accuracy factor from the percent recoveries for each selected constituent. The reciprocal of the lower of the two recovery values divided by 100, yields the accuracy factor. The corrected concentration for each sample set is obtained by multiplying the accuracy factor by the uncorrected data value. The calculation of recovery values is described in Section 1 of this background document. The actual recovery values and accuracy factors for the selected constituents are presented in Appendix E. The accuracy factors calculated for the selected constituents varied from a high value of 4.76 for phenol to a low value of 0.87 for nitrobenzene. The corrected concentration values for the selected constituents are shown for the four data 6-3 Rev. 3 ------- sets in Table 6-1. These corrected concentration values were obtained by multiplying the accuracy factors (Appendix E) by the concentration values for the selected constituents in the treated waste. An arithmetic average value, representing the treated waste concentration, was calculated for each selected constituent from the four corrected values. These averages are presented in Table 6-1. 6.3 Calculating Variability Factors It is expected that in normal operation of a well-designed and well-operated treatment system there will be some variability in performance. Based on the test data, a measure of this variability is expressed by the variability factor (see Appendix A). These factors were calculated for each of the selected regulated constituents. The methodology for calculating variability factors is explained in Appendix A of this report. Table 6-1 presents the results of calculations for the selected constituents. Appendix D of this report shows how the actual values in Table 6-1 were calculated. The variability factors calculated for the selected constituents vary from a high value of 15.40 for aniline to a low value of 1.65 for 2,4-dinitrophenol. A variability factor of 1.0 represents test data from a process measured without variation and analytical interferences. Nitrobenzene was not detected in 6-4 Rev. 3 ------- (A L. 41 I IA ID 2 ^ ^ (0 ro 0 o M •o 1 £1 E CO — • a u- » TJ -^ i- > CO C TO 41 41 CO E > X t- 4J ^ it X 4-» _• L. •^ o ^* .a 4-» u. CO U > "- ID ^^ ID g 4> T> '£ ~ O) 41 41 CO — • CO 4-< 4J 1- ^x t- co IA 4-> m 41 41 CO C E > l- 3 41 ^ < 1— O u f- 4) g i h § CO 4> s 4) IU 4* u to w o 0 p V CU (M 4V — . % 8 fr « 1- CO 4) 1. CO (A o o 1 X u i i* u e • U CO 4) < CO CO v 3 4V u K 0 - in 0 -* •» co >O ro in in o o^ ru co 0 C\J a o in O «- in o o CO • ~ • - r e o § i " ro 5 0 co ^ «~ CM ro o ^ CM CO O CM 0 CD -O ^» CM «- o rv 0 0 >o ro CM NJ- o «- 0 0 •o ro CM st o «- o o ^ ro CM ~» o «- C> 0 « 41 N v C 4> ° 1 L. C 4v CD ••- x: z a. T- «- CM ^j' ro fO tn s in o S 0 f^. CM O o s o s o 41 # (/) * 'i X o (A ID O 4-> 0 C 1- CO 0 u • I 1 , a X < c CA 3 U IA TJ tfl CO 1 determi 41 i. 3 01 o u CO u. X 4-* !5 a L. a i (A O u u. § 4-* l_ S X u ID D U u - § •j § ^ 2 'c a CM C_ 0 H- •o t. CO CO IA 41 4-> H- o g 4-« CO 3 U CO o 41 JC. 4.1 C IA 3 8 3 1 f 4-> f ^_ O X 1 z u £ u L. U a. * ( 1 g y \| "8 4-» CO O) " 41 u CO ta * 'E CD X CD 4-1 O I— ; 6-5 Rev. 3 ------- the treated waste, and concentration values for the treated waste were set at the Practical Quantification Level for nitrobenzene. This resulted in no apparent variation among the treated values and a calculated variability factor of 1.0. Instead of using the calculated value of 1.0, the variability factor for nitrobenzene was fixed at 2.8 as justified in Appendix D of this document. 6.4 Calculating the Treatment Standards The treatment standards for the selected constituents were calculated by multiplying the variability factors by the average concentration values for the treated waste. The treatment standards are presented in Table 6-1. Standards were calculated for wastewaters only. The treatment standards for K103 and K104 nonwastewaters are transferred from the treatment tests of K019 and K048/K051 wastes. The BDAT Wastewater Treatment Standard for waste code K103 is as follows: Constituent Total Composition (mg/1) Benzene 0.147 Aniline 4.450 2,4-Dinitrophenol 0.613 Nitrobenzene 0.Q7 3 Phenol 1.391 6-6 Rev. 3 ------- The BOAT Wastewater Treatment Standard for waste code K104 is as follows: Constituent Total Composition (inq/1) Benzene 0.147 Aniline 4.450 2,4-Dinitrophenol 0.613 Nitrobenzene 0.073 Phenol 1.391 Total Cyanides (CN) 2.683 The treatment standards for waste codes K103 and K104 vary from 4.45 mg/1 for aniline to 0.073 mg/1 for nitrobenzene. Nonwastewater treatment standards for waste codes K103 and and K104 were also determined by the Agency. These treatment standards apply to the spent carbon from the carbon adsorber; these treatment standards do not apply to the nitrobenzene solvent from the liquid/liquid extractor because the Agency believes that no ash is formed when this stream is incinerated. No performance data were available for the treatment of K103 and K104 nonwastewaters. The Agency therefore decided to transfer treatment standards from the treatment of wastes which were determined to be similar to K103 and K104 nonwastewaters based on waste characteristics affecting „performance. The nonwastewater treatment standards for waste codes K103 and K104 were transferred from treatment data for wastes K019 and K048/K051. The thermal conductivities of wastes K019, K048, and 6-7 Rev. 3 ------- K051 were compared with the thermal conductivities of waste codes K103 and K104. Waste K019 was selected for transferring treatment standards to wastes K103 and K104 because its thermal conductivity was lower than that of both wastes K103 and K104. The treated waste concentrations and treatment standards for K019 are presented in Table 6-2. The boiling points of the selected constituents in waste codes K103 and K104 were compared to the boiling points of the regulated constituents in waste code K019. Constituents were matched as closely as possible on the basis of the boiling point (see Table 6-2). Chlorinated organic constituents in K019 with three or more chlorine atoms in their structure were eliminated from consideration for this matching. All chlorinated organics with three or more chlorine atoms were below detectable levels in treated K019. The treated concentrations were therefore set at the detection limit for these constituents. However, the detection limits for these constituents were abnormally high in treated K019 due to matrix interferences, leading to high treatment standards. Therefore, chlorinated organic constituents with three or more chlorine atoms were not considered when matching constituents from K103 and K104 with those from K019. The remaining constituents in K019 were matched as closely as V possible with those in K103 and K104 on the basis of boiling 6-8 Rev. 3 ------- 0) 01 4-* CO 3 OJ 4-1 at o z o o i* L. 0 H- CO •a i CO 4-* 1: 4-> 2 i_ "8 (U J CD 3 O m (j TJ e 4J V) i o 1? CD g~ O ^J 2 (0 1— y-% O) CJ c ** •^ c • -• -i- o) o £ * CD v-* +•• "O 41 C i— ^"* O) E -n ^ i_ uT +•* C ^^ CO > w co ro > 0) 4-> E < X t. C/> w v^ )— X 4V !^ O " • r- 4V U- -O O > co a w ••- U. L. CO > 0) V 4V ^ O) 4^ CU 10 O) ID O 4-» t_ ^ t, 01 CO 4-> «v S t S g If •to o v 0 C o U g T3 4-» ^N (5 o> co oi ai 4J IS L. D) -^ 10 CO 4-> C -^ Q> ID c co ro i- 3 0) o: £ 1- 0 ^ c o CJ 4J i 4>* 4J S U N- in - in CM • • «- • eo o«-"-«-«- or~-oO>>o CMCMCMPJCM »-O«-«~ CO C 01 X 01 JJ JI 0) O £ C O 4-> ^ L. 4-» CO t- 01 01 W O 0) £ O c o oi — • O4-> oi— > 01 UOf t-0)0)Cf M e o i- o oocvu c E — o •- -. i_ « «. — 01 O -C — U •• * .C O — • £ C_ ^H-O^h- V) O— 'I04JI— oo— oi oi ijz.c:ci I.UOID— — ' CMU4-TO>4> .. o o i i- - — ^to.cc- ty) — • ^* CM 4-» i— v toxo.O)CM 0) _C^»0» CO '-0)IOJC* — ' O O «- 1— «— — • CO^ZCi.«— 0 4J > — • OvtrocMin 6 ooro«-'-o o «-iM*^t j in > m .-.-•-«- £ 01 4- CO 2 01 01 t-- 1 1 ~ c • -& 1 c ^ i; "S H- CD o> ro 4-> O c ^> X O •f- 4-1 i. . 1 l> O -Q «- <-• c o to W! 0> 4J 5 to t- -o O 4J en 42 C !c 4V 02 to E X- tu g i ~ o E o> L. C * 8 -c D -S L. o co oi 1- H- CJ 01 CO -^ U C O 01 CO CO X t. CO V CO 0) - C -C C t- -v -S 0 BM- 0) 01 — • -C t_ ca 4J oi O £ S4-I t- > 01 CD 0) t- ? r S (0 01 4V i (0 CO 4V X C 4V O 0) C C 3 0) 01 4V e o> — 4V < 4V CO 10 01 01 C e- j= O 1— t- O CM 6-9 Rev. 3 ------- point.1 Treatment standards were then transferred from waste code K019 to the matched constituent. Cyanide treatment standards were transferred from the treatment of K048/K051, since cyanide was not present in K019 waste. The BDAT nonwastewater treatment standards for waste codes K103 and K104 are as follows: Total Composition Constituent Benzene Aniline 2,4-Dinitrophenol Nitrobenzene Phenol Total Cyanides (CN) NR - Not regulated for this waste code. K104 5.96 5.44 5.44 5.44 5.44 1.48 1. The removal of highly chlorinated organic constituents in K019 from consideration for transfer affected the treatment standards for the following constituents in K103 and K104: nitrobenzene (naphthalene was used rather than 1,2,4-tri- chlorobenzene), aniline, and phenol (naphthalene was used rather than hexachloroethane or 1,2,4-trichlorobenzene). 6-10 Rev. 3 ------- 7. CONCLUSIONS The Agency has proposed treatment standards for waste codes K103 and K104 generated by the nitrobenzene/aniline industry. Standards for wastewater and nonwastewater forms of these wastes are presented in Tables 7-1 and 7-2 respectively. The treatment standards proposed for waste code K103 and K104 have been developed consistent with EPA's promulgated methodology for BOAT (November 7, 1986, 51 FR 40572). Both waste codes are generated by the treatment of process wastewaters from the nitrobenzene/aniline industry. Based on a careful review of available data for the industrial processes which generate these wastes and all available data characterizing these wastes, the Agency has determined that these two waste codes represent a separate waste treatability group. Wastes in this treatability group are primarily comprised of water, with nitrobenzene or aniline present in smaller but significant quantities. Although the concentrations of specific constituents will vary from facility to facility, all of the wastes are expected to contain similar BDAT list organics and are expected to be treatable to the same levels using the same technology. V- The BDAT list constituents generally present in wastes of this treatability group are benzene, aniline, 2,4-dinitrophenol, nitrobenzene, phenol, and cyanides. Additionally the Agency 7-1 Rev. 3 ------- TABLE 7-1 BOAT TREATMENT STANDARDS FOR WASTEWATER: K103 AND K104 WASTES Regulated Constituents Total Composition (mg/1) K103 K104 Benzene Aniline 2 , 4-Dinitrophenol Nitrobenzene Phenol Total Cyanides 0.147 4.450 0.613 0.073 1.391 NR 0.147 4.450 0.613 0.073 1.391 2.683 NR - Not regulated for this waste code. TABLE 7-2 BOAT TREATMENT STANDARDS FOR NONWASTEWATER: K103 AND K104 WASTES Regulated Constituents Total Composition (mg/kg) K103 K104 Benzene 5.96 5.96 Aniline 5.44 5.44 2,4-Dinitrophenol 5.44 5.44 Nitrobenzene 5.44 5.44 Phenol 5.44 5.44 Total Cyanides NR 1.48 NR - Not regulated for this waste code. 7-2 Rev. 3 ------- expects that these wastes could be mixed together prior to treatment. As a result, EPA has examined the sources of the wastes, applicable technologies, and waste treatment performance in order to support a single regulatory approach for these six waste constituents. Through available data bases, the Agency has identified the following demonstrated technologies for treatment of constituents present in the wastes which are part of this treatability group: solvent (liquid/liquid) extraction, steam stripping, activated carbon adsorption, and biological treatment. In the development of treatment standards for these wastes, the Agency examined all available treatment data. The Agency also conducted performance tests on a commercial scale treatment system consisting of liquid/liquid extraction followed by steam stripping and activated carbon adsorption for waste codes K103 and K104. Design and operating data collected during the testing of the treatment system indicate that the treatment system was properly operated during four of the five sample sets. Accordingly, the treatment performance data from four sample sets were used in the development of the BOAT treatment standards. Two categories of treatment standards were developed for wastes in the K103 and K104 treatability group: wastewater and • nonwastewater wastes. (For the purpose of the land disposal restrictions rule, wastewaters are defined as wastes containing 7-3 Rev. 3 ------- less than 1% by weight filterable solids and less than 4% by weight total organic carbon. For K103 and K104 wastes, this definition was amended to include wastewaters with a TOC content up to 4%). BOAT for the wastewater forms of waste codes K103 and K104 was determined to be liquid/liquid extraction followed by steam stripping and activated carbon adsorption. This was based on a statistical comparison of the Agency's test and performance data from this treatment train to other available treatment data. The wastewater treatment standards for waste codes K103 and K104 are based on EPA's test of liquid/liquid extraction followed by steam stripping and activated carbon adsorption. Two nonwastewater forms of waste codes K103 and K104 were identified by the Agency as spent carbon from the activated carbon adsorber and nitrobenzene solvent from the nitrobenzene liquid/liquid extractor. Incineration was determined to be BOAT for the nonwastewater forms of wastes K103 and K104. Nonwastewater treatment standards for K103 and K104 are based on a transfer of treatment data from K019 and K048/K051 wastes. BOAT for wastes K019 and K048/K051 was determined to be rotary kiln incineration. Treatment data for BDAT list organics were transferred from waste KOI9 based on a comparison of the thermal conductivities between waste code 7-4 Rev. 3 ------- K019 and waste codes K103 and K104. Data were transferred for constituents selected for regulation on a constituent by constituent basis. This was done by matching constituents on the basis of boiling points. Treatment standards for cyanide were transferred from the treatment of K048/K051, since cyanide was not present in K019 waste. Nonwastewater standards are established only for the spent carbon from the activated carbon adsorber because the Agency believes that the incineration of the nitrobenzene solvent from the nitrobenzene liquid/liquid extractor will not produce ash. The transfer of data for these nonwastewaters was determined to be appropriate due to the similarity in physical and chemical composition of the wastes such that the wastes would be expected to be treated to similar levels by the same technology. Regulated constituents were selected on the basis of substantial treatment, which was determined by comparing the constituent concentrations detected in the untreated and treated wastes. All waste characterization data and applicable treatment data consistent with the type and quality of data needed by the Agency in this program were used to make this determination. For waste codes K103 and K104, the regulated constituents also represent the BDAT list constituents present at the highest concentrations. However, if the performance data for the technology selected as BDAT indicated that the constituent was 7-5 Rev. 3 ------- not significantly treated, then that constituent was not regulated. Some constituents present at treatable concentrations in the untreated waste were not regulated if it was determined that they would be adequately controlled by regulation of another constituent. Treatment standards for these wastes were derived after correction of laboratory data to account for recovery (Section 6). Subsequently, the mean of the corrected data points was multiplied by a variability factor to derive the standards. The variability factor corrects the lab data for reasonable variations measured in the treatment process and imprecision in sampling and analytical methods. Variability factors were determined using a statistical method which accounts for variability in the results for a number of data points for a given constituent. A variability factor of 2.8 was chosen for constituents for which a specific variability factor could not be calculated (See Appendix A for justification). Wastewater and nonwastewater forms of waste codes K103 and K104 may be land disposed if they meet the concentration standards at the point of disposal. The BDAT technology upon which the treatment standards are based (liquid/liquid extraction followed by steam stripping and activated carbon adsorption for wastewater, and incineration for nonwastewater) need not be specifically utilized prior to land disposal, provided that the 7-6 Rev. 3 ------- actual technology utilized meets the standard, does not involve dilution or other methods deemed unacceptable by the Agency, and does not pose a greater risk to human health and the environment than land disposal. These standards become effective as of August 8, 1988, as per the schedule set forth in 40 CFR 268.10. The Agency estimates that there is a lack of nationwide treatment capacity at this time for the nonwastewater forms of waste codes K103 and K104. Therefore, the Agency has proposed to grant a 2-year nationwide variance to the effective date of the land disposal ban for these wastes. A detailed discussion of the Agency's determination that a lack of nationwide incineration capacity exists is presented in the Capacity Background Document which is available in the Administrative Record for the First Sixths' Rule. Consistent with Executive Order 12291, EPA prepared a regulatory impact analysis (RIA) to assess the economic effect of compliance with this proposed rule. The RIA prepared for this proposal rule is available in the Administrative Record for the First Sixths' Rule. 7-7 Rev. 3 ------- REFERENCES Ackerman D.G., J.F. McGaughey, D.E. Wagoner, "At Sea Incineration of PCB-Containing Wastes on Board the M/T Vulcanus." USEPA 600/7-83-024, April 1983. Authur D. Little, Inc. (1977). "Physical, Chemical and Biological Treatment Techniques for Industrial Wastes." Vol. I - NTIS PB275-054. pp. 1-1 to 1-18 and 1-37 to 1-41. Bonner T.A., et al., Engineering Handbook for Hazardous Waste Incineration. SW889. Prepared by Monsanto Research Corporation for U.S. EPA, NTIS PB 81-248163. June 1981. De Renzo, D.J. (editor). (1978). Unit Operations for Treatment of Hazardous Industrial Wastes. Noyes Data Corporation, Park Ridge, New Jersey. Enckenfelder, W., et al. (September 2,1985). "Wastewater Treatment." Chemical Engineering. Gallacher, Lawrence V. (February 1981). "Liquid Ion Exchange in Metal Recovery and Recycling." 3rd Conference on Advanced Pollution Control for the Metal Finishing Industry. U.S. EPA 600/2-81-028. pp. 39-41. GCA Corp. (October 1984). Technical Assessment of Treatment Alternatives for Wastes Containing Halogenated Organics. Prepared for USEPA, Contract 68-01-6871. pp. 150-160. Hackman, Ellsworth. (1978). Toxic Organic Chemicals. Destruction and Waste Treatment. Noyes Data Corporation, Park Ridge, New Jersey, pp. 109-111. Hanson, Carl. (August 26, 1968). "Solvent Extraction Theory, Equipment, Commercial Operations, and Economics." Chemical Engineering, p. 81. Hutchins, R. (1979) . "Activated Carbon Systems for Separation of Liquids." pp. 1-415 through 1-486 as published in Handbook of Separation Techniques for Chemical Engineers. Philip A. Schweitzer (editor). McGraw-Hill. Humphrey, Jimmy L., J. Antonia Rocha, and James R. Fair. (September 17, 1984). "The Essentials of Extraction." Chemical Engineering, pp. 76-95. Kirk & Othmer. (1965). Encyclopedia of Chemical Technology. 2nd ed., Vol. 7, John Wiley and Sons, New York. pp. 204- 248. Rev. 3 ------- REFERENCES (Continued) Kirk & Othmer. Encyclopedia of Chemical Technology. Volume 2 (p. 37-361), Vol. 15 (p. 916-925). Ku, W. and Peters, R.W. (May 1987). "Innovative Uses or Carbon Adsorption of Heavy Metals from Plating Wastewaters: I. Activated Carbon Polishing Treatment." Environmental Progress. Lo, Teh C., Malcolm H. I. Baird, and Carl Manson (editors). 1983. Handbook of Solvent Extraction. John Wiley and Sons. New York. pp. 53-89. McCabe, Warren L., Julian C. Smith, and Peter Harriot. (1985). Unit Operations of Chemical Engineering. McGraw-Hill Book Company, New York. pp. 533-606. Metcalf and Eddy Inc. (1985). "Briefing, Technologies Applicable to Hazardous Waste." Prepared for USEPA, ORD, HWERL. Section 2.13. Mitre Corp. "Guidance Manual for Waste Incinerator Permits." NTIS PB84-100577. July 1983. Novak R.G., W.L. Troxler, T.H. Dehnke, "Recovering Energy from Hazardous Waste Incineration." Chemical Engineering Progress 91:146 (1984). Oppelt E.T., "Incineration of Hazardous Waste." JAPCA, Volume 37, No. 5. May 1987. Patterson, J. (1985). Industrial Wastewater Treatment Technology. 2nd ed., Butterworth Pub. pp. 329-340. Perry, Robert H. and Cecil H. Chilton. (1973). Chemical Engineer's Handbook. 5th edition. McGraw-Hill Book Company, New York. pp. 13-1 to 13-60 and pp. 15-1 to 15-24. Rose, L.M. (1985). Distillation Design in Practice. Elsevier, New York. pp. 1-307. Santoleri J.J., "Energy Recovery-A By-Product of Hazardous Waste Incineration Systems." In Proceedings of the 15th Mid- Atlantic Industrial Waste Conference, on Toxic and Hazardous Waste, 1983. SRI. (1985). Stanford Research Institute. Chemical Economics Handbook (CEH). Menlo Park. California. Rev. 3 ------- REFERENCES (Continued) Touhill, Shuckrow & Assoc. (February 1981). "Concentration Technologies for Hazardous Aqueous Waste Treatment." NTIS PB81-150583. pp. 53-55. U. S. Environmental Protection Agency. (May 1981). Identification and Listing Hazardous Waste under RCRA.^ Subtitle C. Section 3001. Background Document. U.S. EPA. (1987). Onsite Engineering Report of Treatment Technology Performance and Operation for E.I, du Pont de Nemours & Co.. Inc. - Beaumont. TX. USEPA (October 1973). Process Design Manual for Carbon Adsorption. NTIS PB227-157. pp. 3-21 and 53. USEPA (1986). Best Demonstrated Available Technology (BOAT) Background Document for F001-F005 Spent Solvents, Vol. 1. EPA/530-SW-86-056, November, 1986. Van Winkle, Matthew. (1967). Distillation. McGraw-Hill Book Company, New York. pp. 1-684. Versar (1985). Versar, Inc. An Overview of Carbon Adsorption. Draft Final Report. U.S. Environmental Protection Agency: Exposure Evaluation Division Office of Toxic Substances, Washington, D.C. EPA Contract No. 68-02-3968, Task No. 58. Vogel G., et al., "Incineration and Cement Kiln Capacity for Hazardous Waste Treatment." In Proceedings of the 12th Annual Research Symposium. Incineration and Treatment of Hazardous Wastes. Cincinnati, Ohio. April 1986. Water Chemical Corporation. (August 1984). Process Design Manual of Stripping of Organics. NTIS PB84-232628. Prepared for the Industrial Environmental Research Laboratory Office of Research and Development, U.S. Environmental Protection Agency, pp. 1-1 to F4. Rev. 3 ------- APPENDIX A - STATISTICAL ANALYSIS A.1 F Value Determination for ANOVA Test As noted earlier in Section 1.0, EPA is using the statistical method known as analysis of variance in the determination of the level of performance that represents "best" treatment where more than one technology is demonstrated. This method provides a measure of the differences between data sets. If the differences are not statistically significant, the data sets are said to be homogeneous. If the Agency found that the levels of performance for one or more technologies are not statistically different (i.e., the data sets are homogeneous), EPA would average the long term performance values achieved by each technology and then multiply this value by the largest variability factor associated with any of the acceptable technologies. If EPA found that one technology performs significantly better (i.e., the data sets are not homogeneous), BOAT would be the level of performance achieved by the best technology multiplied by its variability factor. To determine whether any or all of the treatment performance ------- values are available in most statistics texts (see, for example, Statistical Concepts and Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications, New York). Where the F value is less than the critical value, all treatment data sets are homogeneous. If the F value exceeds the critical value, it is necessary to perform a "pair wise F" test to determine if any of the sets are homogeneous. The "pair wise F" test must be done for all of the various combinations of data sets using the same method and equation as the general F test. The F value is calculated as follows: (i) All data are natural logtransformed. (ii) The sum of the data points for each data set is computed (T.). (iii) The statistical parameter known as the sum of the squares between data sets (SSB) is computed: SSB • A k I 1-1 '^_' ni _ r k i-1 Tl N Z where: k = number of treatment technologies n. = number of data points for technology i N = number of data points for all technologies T. = sum of natural logtransformed data points for each technology. Appendix A-2 Rev. 3 ------- (iv) The sum of the squares within data sets (SSW) is computed: SSW = • k I j; x2, ,j k - I 1-1 '!L ni . where: x. . = the natural logtransformed observations (j) for '-1 treatment technology (i) . (v) The degrees of freedom corresponding to SSB and SSW are calculated. For SSB, the degree of freedom is given by k-1. For SSW, the degree of freedom is given by N-k. (vi) Using the above parameters, the F value is calculated as follows: where: MSB = SSB/(k-1) and MSW = SSW/(N-k). MSB F = MSW Appendix A-3 Rev. 3 ------- A computational table summarizing the above parameters is shown below. Computational Table for the F Value Source Between Within Degrees of freedom K-l N-k Sum of squares SSB SSW Mean square MSB = SSB/k-1 MSW = SSW/N-k F MSB/MSW Below are three examples of the ANOVA calculation. The first two represent treatment by different technologies that achieve statistically similar treatment; the last example represents a case where one technology achieves significantly better treatment than the other technology. Appendix A-4 Rev. 3 ------- Table A-l F Distribution at the 95 Percent Confidence Level ro n Denominator degrees ol freedom 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 40 60 >20 QO 16T 4 1851 10 13 7 71 661 599 559 5,32 5.12 496 484 475 467 460 454 449 445 441 438 435 432 430 428 426 424 423 421 420 418 417 408 400 392 3.84 2 1995 1900 955 694 579 514 4 74 446 426 4 10 398 389 381 374 368 363 359 355 352 349 347 344 3.42 340 339 337 335 334 333 3.32 323 3.15 3.07 3.00 3 2157 1916 923 659 541 476 435 407 3.86 3.71 359 349 341 334 329 324 320 316 313 310 307 305 303 301 299 298 296 295 2.93 292 2.84 2.76 2.68 2.60 Numerator degrees ol freedom 4567 2246 1925 912 639 5.19 453 412 3.84 363 348 336 3.26 3.18 311 306 301 296 293 290 287 284 282 280 2.78 276 274 273 271 2.70 269 2.61 253 245 2.37 2302 1930 901 626 5.05 439 397 3.69 3.48 3.33 3.20 311 3.03 2.96 290 2.85 281 2.77 274 2.71 2.68 266 2.64 262 260 259 257 256 255 253 2.45 237 229 2.21 2340 1933 894 616 495 428 3.87 358 337 3.22 3.09 3.00 2.92 2.85 2.79 2.74 2.70 266 2.63 260 2.57 2.55 2.53 251 249 247 246 2.45 243 242 2.34 225 2.17 2.10 236.8 1935 889 6.09 488 421 3.79 3.50 3.29 3.14 3.01 2.91 2.83 2.76 2.71 266 2.61 258 2.54 2.51 249 2.46 244 242 2.40 2.39 2.37 2.36 2.35 2.33 2.25 2.17 2.09 2.01 a 2389 1937 885 604 482 415 3.73 3.44 323 3.07 2.95 2.85 2.77 2.70 2.64 2.59 2.55 2.51 2.48 2.45 2.42 2.40 2.37 2.36 234 2.32 231 2.29 2.28 2.27 2.18 2.10 2.02 194 9 2405 1938 881 600 477 410 368 339 3.18 3.02 2.90 280 2.71 2.65 259 254 249 246 242 239 237 234 232 2.30 228 2.27 225 2.24 2.22 221 212 204 196 1 88 Appendix A-5 Rev. 3 ------- Example 1 Methytene Chloride Steam stripping Influent (mg/l) 1550.00 1290.00 1640.00 5100.00 1450.00 4600.00 1760.00 2400.00 4800.00 12100.00 Effluent (mg/l) 10.00 10.00 10.00 12.00 10.00 10.00 10.00 10.00 10.00 10.00 In(effluent) 2.30 2.30 2.30 2.48 2.30 2.30 2.30 2.30 2.30 2.30 2 [ln(ef fluent)] 5.29 5.29 5.29 6.15 5.29 5.29 5.29 5.29 5.29 5.29 Influent (mg/l) 1960.00 2568.00 1817.00 1640.00 3907.00 Biological treatment Effluent In(effluent) (mg/l) 10.00 2.30 10.00 2.30 10.00 2.30 26.00 3.26 10.00 2.30 2 [ln( effluent)] 5.29 5.29 5.29 10.63 5.29 Sun: 23.18 53.76 12.46 31.79 Sample Size: 10 10 Mean: 3669 10.2 Standard Deviation: 3328.67 .63 Variability Factor: 1.15 10 2.32 .06 2378 923.04 13.2 7.15 2.48 2.49 .43 ANOVA Calculations: SSB III!! f>i A SSW < MSB = SSB/(k-1) HSU = SSW/(N-k) '' t _ i-l I n, Appendix A-6 Rev. 3 ------- Example 1 (continued) F = MSB/HSW where: k = number of treatment technologies n. = number of data points for technology i N = nunber of natural log transformed data points for all technologies T. = sum of log transformed data points for each technology X = the nat. log transformed observations (j) for treatment technology (i) i i ni = 10, n = 5, N = 15, k = 2, T = 23.18, T = 12.46, T = 35.64, T = 1270.21 T = 537.31 T = 155.25 cco SSB 537.31 155.25 10 1270.21 15 0.10 SSWM53.76.31.79)-!537'31.155-25' 10 0.77 MSB = 0.10/1 = 0.10 MSW = 0.77/13 = 0.06 0.10 F = 0.06 1.67 ANOVA Table Degrees of Source freedom Between(B) 1 Within(U) 13 SS MS F 0.10 0.10 1.67 0.77 0.06 The critical value of the F test at the 0.05 significance level is 4.67. Since the F value is less than the critical value, the means are not significantly different (i.e., they are homogeneous). „ Note: All calculations were rounded to two decimal places. Results may differ depending upon the number of decimal places used in each step of the calculations. Appendix A-7 Rev. 3 ------- Example 2 Trichloroethylene Steam stripping Influent (mg/O 1650.00 5200.00 5000.00 1720.00 1560.00 10300.00 210.00 1600.00 204.00 160.00 Effluent (mg/D 10.00 10.00 10.00 10.00 10.00 10.00 10.00 27.00 85.00 10.00 In(effluent) 2.30 2.30 2.30 2.30 2.30 2.30 2.30 3.30 4.44 2.30 2 [ln(ef fluent)] 5.29 5.29 5.29 5.29 5.29 5.29 5.29 10.89 19.71 5.29 Biological treatment Influent (mg/l) 200.00 224.00 134.00 150.00 484.00 163.00 182.00 Effluent (mg/l) 10.00 10.00 10.00 10.00 16.25 10.00 10.00 ln( effluent) 2.30 2.30 2.30 2.30 2.79 2.30 2.30 2 [ln( effluent)] 5.29 5.29 5.29 5.29 7.78 5.29 5.29 Sum: Sample Size: 10 10 Mean: 2760 19.2 Standard Deviation: 3209.6 23.7 Variability Factor: 3.70 26.14 10 2.61 .71 72.92 220 120.5 10.89 2.36 1.53 16.59 2.37 .19 39.52 ANOVA Calculations: SSB U- 1=1 n, ssw . MSB = SSB/(k-1) MSW = SSW/(N-k) r k Appendix A-8 Rev. 3 ------- Example 2 (continued) f = HSB/HSW where: k = number of treatment technologies n. = number of data points for technology i N = number of data points for all technologies T. = sum of natural log transformed data points for each technology X = the natural log transformed observations (j) for treatment technology (i) M = 10, N = 7, N = 17, k = 2, T = 26.14, T = 16.59, T = 42.73, T = 1825.85. T = 683.30, ^2 = 275.23 .S8 J683_30 + 275.MJ _ 1K5.B5 = 0_25 i 10 7 j 17 SSW » (72.92 > 39.52, - ""•'" * ""I = 4.79 ( 10 7 MSB = 0.25/1 = 0.25 MSW = 4.79/15 = 0.32 F = °' = 0.78 0.32 ANOVA Table Degrees of Source freedom Between(B) 1 Uithin(W) 15 SS MS F 0.25 0.25 0.78 4.79 0.32 The critical value of the F test at the 0.05 significance level is 4.54. Since the F value is less than the critical value, the means are not significantly different (i.e., they are homogeneous). Note: All calculations were rounded to two decimal places. Results may differ depending upon the number of decimal places used in each step of the calculations. Appendix A-9 Rev. 3 ------- Example 3 Chlorobenzene Activated sludge followed Influent (mg/l) 7200.00 6500.00 6075.00 3040.00 Effluent (mg/l) 80.00 70.00 35.00 10.00 by carbon adsorption Biological treatment 2 ' In(effluent) [ln(eff luent)] Influent (mg/l) 4.38 19.18 9206.00 4.25 18.06 16646.00 3.56 12.67 49775.00 2.30 5.29 14731.00 3159.00 6756.00 3040.00 Effluent (mg/l) 1083.00 709.50 460.00 142.00 603.00 153.00 17.00 ln( effluent) 6.99 6.56 6.13 4.96 6.40 5.03 2.83 2 In [(effluent)] 48.86 43.03 37.58 24.60 40.96 25.30 8.01 Sum: Sample Size: 4 4 Mean: 5703 49 Standard Deviation: 1835.4 32.24 Variability Factor: 7.00 14.49 55.20 3.62 .95 14759 16311.86 452.5 379.04 15.79 38.90 228.34 5.56 1.42 ANOVA Calculations: SSB - "1 z, r, ssw MSB = SSB/(k-1) MSU = SSW/(N-k) F = MSB/MSW r k T,2 Appendix A-10 Rev. 3 ------- Example 3 (continued) where, k = number of treatment technologies n. = number of data points for technology i N = number of data points for all technologies T. = sum of natural log transformed data points for each technology X.. = the natural log transformed observations (j) for treatment technology (i) N = 4, N = 7, N = 11, k = 2, T = 14.49, T = 38.90, T = 53.39, T = 2850.49, T = 209.96 I2 = 1513.21 SSB »l + \| - = 9.52 11 =14.88 SSW - (55.20 * 228.34) - MSB = 9.52/1 = 9.52 MSW = 14.88/9 = 1.65 F = 9.52/1.65 = 5.77 ANOVA Table Degrees of Source freedom SS MS Between(B) Uithin(U) 1 9 9.53 14.89 9.53 1.65 5.77 The critical value of the F test at the 0.05 significance level is 5.12. Since the F value is larger than the critical value, the means are significantly different (i.e., they are heterogeneous). Note: All calculations were rounded to two decimal places. Results may differ depending upon the number of decimal places used in each step of the calculations. Appendix A-ll Rev. 3 ------- A.2. Variability Factor C99 VF = Mean where: VF = estimate of daily maximum variability factor determined from a sample population of daily data. C = Estimate of performance values for which 99 percent of the daily observations will be below. C 9 is calculated using the following equation: C = Exp(y +2.33 Sy) where y and Sy are the mean ana standard deviation, respectively, of the logtransformed data. Mean = average of the individual performance values. EPA is establishing this figure as an instantaneous maximum because the Agency believes that on a day-to-day basis the waste should meet the applicable treatment standards. In addition, establishing this requirement makes it easier to check compliance on a single day. The 99th percentile is appropriate because it accounts for almost all process variability. In several cases, all the results from analysis of the residuals from BOAT treatment are found at concentrations less than the detection limit. In such cases, all the actual concentration values are considered unknown and hence, cannot be used to estimate the variability factor of the analytical results. Below is a description of EPA's, approach for calculating the variability factor for such cases with all concentrations below the detection limit. Appendix A-12 Rev. 3 ------- It has been postulated as a general rule that a lognormal distribution adequately describes the variation among concentrations. Therefore, the lognormal model has been used routinely in the EPA development of numerous regulations in the Effluent Guidelines program and is being used in the BDAT program. The variability factor (VF) was defined as the ratio of the 99th percentile (Cgg) of the lognormal distribution to its arithmetic mean (Mean). VF = ^99 (1) Mean The relationship between the parameters of the lognormal distribution and the parameters of the normal distribution created by taking the natural logarithms of the lognormally-distributed concentrations can be found in most mathematical statistics texts (see for example: Distribution in Statistics-Volume 1 by Johnson and Kotz, 1970). The mean of the lognormal distribution can be expressed in terms of the mean (JJL ) and standard deviation ( Q- ) of the normal distribution as follows: C9g = Exp ( JU + 2.3340-) (2) Mean = Exp ( Jj^ + .54 ------- VF = Exp (2.33 d - .54cr2) (4) For residuals with concentrations that are not all below the detection limit, the 99th percentile and the mean can be estimated from the actual analytical data and accordingly, the variability factor (VF) can be estimated using equation (1) . For residuals with concentrations that are below the detection limit, the above equations can be used in conjunction with the assumptions below to develop a variability factor. Step 1: The actual concentrations follow a lognormal distribution. The upper limit (UL) is equal to the detection limit. The lower limit (LL) is assumed to be equal to one tenth of the detection limit. This assumption is based on the fact that data from well-designed and well-operated treatment systems generally falls within one order of magnitude. Step 2: The natural logarithms of the concentrations have a normal distribution with an upper limit equal to In (UL) and a lower limit equal to In (LL) . Step 3: The standard deviation (CT ) of the normal distribution is approximated by * CT = [(In (UL) - In (LL) ] / [(2) (2.33)] = [ln(UL/LL)] /4.66 when LL = (0.1) (UL) then ------- Step 4: Substitution of the value from Step 3 in equation (4) yields the variability factor, VF. VF = 2.8 Appendix A-15 Rev. 3 ------- APPENDIX B - ANALYSIS OF VARIANCE TESTS ANOVA #1 Comparison of L/L Extraction with L/L Extraction Followed by Steam Stripping Compare sample point SD-5 (Untreated Waste to Steam Stripper) with sample point SD-6 (Treated Waste From Steam Stripper) Regulated Constituents: Benzene Nitrobenzene 2,4-Dinitrophenol Phenol Aniline Cyanide Regulated Constituents Present in Untreated Waste (SD-5): Benzene Nitrobenzene Cyanide Regulated Constituents Present in Treated Waste (SD-6): Benzene 2,4-Dinitrophenol () Cyanide - An ANOVA analysis could not be completed on this constituent, since no information is available on the concentration of this constituent in the untreated waste (SD-5). Appendix B - 1 Rev. 3 ------- 1) Benzene (ug/1) AF = 1.32 Raw SD-5 Corr. SD-5 Raw SD-6 Corr. SD-6 170,000 224,400 (5) 6.6 2) Nitrobenzene (ug/1) AF = 0.87 Raw SD-5 Corr. SD-5 Raw SD-6 Corr. SD-6 3) Cyanide (mg/1) AF = 1.39 190,000 250,800 8 10.6 26,000 34,320 (5) 6.6 17,000 22,440 (5) 6.6 2.3X106 2.0X106 (3000) 2610 2.8X106 2.4X106 (3000) 2610 2.0X106 1.7X106 (1500) 1305 2.0X106 1.7X106 (3000) 2610 Raw SD-5 4.36 Corr. SD-5 6.06 Raw SD-6 4.77 Corr. SD-6 6.63 3.45 4.80 3.87 5.38 2.54 3.53 2.08 2.89 2.27 3.16 1.70 2.36 Note: Numbers in parentheses indicate that the compound was not detected in this sample. The detection limit has been used in place of the actual value for this compound. (Above raw values are taken from the EPA's Onsite Engineering Report for K103 and K104. Tables 6-10 and 6-11). Appendix B - 2 Rev. 3 ------- 1) Benzene Treatment 1 Treatment 2 x1— x2_ SSI 224,400 6.6 12.32 1.89 SS2 250,800 10.6 12.43 2.36 SS4 34,320 6.6 10.44 1.89 SS5 22,440 6.6 10.02 1.89 k = 2 n^ = 4 n2 = 4 N = 8 SSB = (T12/n1 + T22/n2) - T2/N = (2043.94/4 + 64.48/4) - 2834.5/8 = (510.99 +16.12) - 354.31 = 527.11 - 354.31 = 172.80 MSB = SSB/k-1 = 172.80/1 = 172.80 SSW = E E Xji2 - 527.11 = 531.97 - 527.11 = 4.86 MSW = SSW/N-k = 4.86/6 =0.81 F = MSB/MSW = 172.80/0.81 = 213.3 Fk-l N-k = Fl 6 = 5«" (critical value for 95% confidence) Appendix B - 3 Rev. 3 ------- 2) Nitrobenzene Treatment 1 Treatment 2 _ — -— SSI 2.00X106 2610 14.51 7.87 SS2 2.44X106 2610 14.71 7.87 SS4 1.74X106 1305 14.37 7.17 SS5 1.74X106 2610 14.37 7.87 k = 2 nl = 4 n2 = 4 N = 8 SSB = (T12/n1 + T22/n2) - T2/N = (3359.36/4 + 947.41/4) - 7874.79/8 = (839.84 + 236.85) - 984.35 = 1076.69 - 984.35 = 92.34 MSB = SSB/k-1 = 92.34/1 = 92.34 SSW = E E X£ -j2 - 1076.69 = 1077. l4 - 1076.69 = .45 MSW = SSW/N-k = 0.45/6 =0.08 F = MSB/MSW = 92.34/0.08 = 1154.25 Fk-l,N-k = Fl,6 = 5.99 (critical value for 95% confidence) Appendix B - 4 Rev. 3 ------- 3) Cyanide Treatment 1 Treatment 2 x^ XT SSI 6.06 6.63 1.80 1.89 SS2 4.80 5.38 1.57 1.68 SS4 3.53 2.89 1.26 1.06 SS5 3.16 2.36 1.15 0.86 k = 2 HI = 4 ri2 = 4 N = 8 SSB = (T12/n1 + T22/n2) - T2/N = (33.41/4 + 30.14/4) - 127.01/8 = (8.35 + 7.54) - 15.88 = 15.89 - 15.88 = 0.01 MSB = SSB/k-1 = 0.01/1 =0.01 SSW = E E Xji2 - 15.89 = 16.87 - 15.89 = 0.98 MSW = SSW/N-k = 0.98/6 =0.16 F = MSB/MSW = 0.01/0.16 =0.06 Fk-l N-k ~ Fl 6 = 5-99 (critical value for 95% confidence) Appendix B - 5 Rev. 3 ------- Computational Table for the F Value Constituent Benzene Nitrobenzene Total Cyanides Source Between Within Between Within Between Within Sum of Squares 172.80 4.86 92.34 0.45 0.01 0.98 Degrees of Freedom 1 6 1 6 1 6 Mean Square 172.80 0.81 92.34 0.08 0.01 0.16 F 213.3* 1154.25* 0.06 * - Indicates that the calculated F value exceeds the critical value. Conclusion L/L Extraction followed by steam stripping is more efficient at reducing the concentration of benzene and nitrobenzene in K103/K104 than L/L extraction alone, but is not more efficient at reducing the concentration of total cyanides in K103/K104 than L/L extraction alone. Appendix B - 6 Rev. 3 ------- ANOVA #2 Comparison of L/L Extraction Followed by Steam Stripping with L/L Extraction Followed by Steam Stripping Followed by Activated Carbon Adsorption Compare sample point SD-8 (Untreated Waste to Activated Carbon Adsorption Beds) with sample point SD-9 (Treated Waste from Carbon Adsorption System) Regulated Constituents: Benzene Nitrobenzene 2,4-Dinitrophenol Phenol Aniline Cyanide Regulated Constituents Present in Untreated Waste (SD-8): Benzene Aniline 2,4-Dinitrophenol Phenol Cyanide Regulated Constituents Present in Treated Waste (SD-9): Benzene Aniline 2 f4-Dinitrophenol Phenol Cyanide Appendix B - 7 Rev. 3 ------- 1) Benzene (ug/1) AF = 1.32 Raw SD-8 Corr. SD-8 Raw SD-9 Corr. SD-9 880 1161.60 42 55.44 2) Aniline (ug/1) AF = 1.10 Raw SD-8 Corr. SD-8 Raw SD-9 Corr. SD-9 57000 62700 (30) 33 130 171.60 (5) 6.6 ND ND (30) 33 3) 2,4-Dinitrophenol (ug/1) AF = 1.25 39 51.48 19 25.08 56000 61600 (30) 33 20 26.40 11 14.52 300000 330000 960 1056 Raw SD-8 Corr. SD-8 53000 66250 ND ND 24000 30000 24000 30000 Raw SD-9 380 Corr. SD-9 475 320 400 260 325 230 288 Numbers in parentheses indicate that the compound was not detected in this sample. The detection limit has been used in place of the actual value for this compound. "ND" indicates that this compound was not detected in the untreated waste (SD-8), and hence this reading was not used in the ANOVA calculations. Appendix B - 8 Rev. 3 ------- 4) Phenol (ug/1) AF = 4.76 Raw SD-8 ND 29000 39000 41000 Corr. SD-8 ND 138040 185640 195160 Raw SD-9 (30) (30) (30) 150 Corr. SD-9 142.8 142.8 142.8 714 5) Cyanide (mg/1) AF = 1.39 Raw SD-8 6.850 4.590 3.470 0.952 Corr. SD-8 9.52 6.38 4.82 1.32 Raw SD-9 0.565 0.597 0.156 0.129 Corr. SD-9 0.79 0.83 0.22 0.18 Note: Numbers in parentheses indicate that the compound was not detected in this sample. The detection limit has been used in place of the actual value for this compound. "ND" indicates that this compound was not detected in the untreated waste (SD-8), and hence this reading was not used in the ANOVA calculations. (Above raw values are taken from the EPA's Onsite Engineering Report for K103 and K104. Tables 6-13 and 6-14). Appendix B - 9 Rev. 3 ------- 1) Benzene Treatment 1 Treatment 2 x^ SSI 1161.6 55.4 7.06 4.01 SS2 171.6 6.6 5.15 1.89 SS4 51.5 25.1 3.94 3.22 SS5 26.4 14.5 3.27 2.67 k = 2 nl = 4 n2 = 4 N = 8 SSB = (T^/ni + T22/n2) - T2/N = (377.14/4 + 139.00/4) - 974.06/8 = (94.29 + 34.75) - 121.76 = 129.04 - 121.76 = 7.28 MSB = SSB/k-1 = 7.28/1 =7.28 SSW = E E Xi -j2 - 129.04 = 139.73 - 129.04 = 10.69 MSW = SSW/N-k = 10.69/6 =1.78 F = MSB/MSW = 7.28/1.78 =4.09 Fk-l N-k = Fl 6 = 5«" (critical value for 95% confidence) Appendix B - 10 Rev. 3 ------- 2) Aniline Treatment 1 Treatment 2 SSI 62700 33 11.05 3.50 SS2 ND 33 ND 3.50 SS4 61600 33 11.03 3.50 SS5 330000 1056 12.71 6.96 k = 2 HI = 3 n2 = 4 N = 7 SSB = (T12/n1 + T22/n2) - T2/N = (1210.34/3 + 304.85/4) - 2730.06/7 = (403.45 + 76.21) - 390.01 = 479.66 - 390.01 = 89.65 MSB = SSB/k-1 = 89.65/1 = 89.65 SSW = E E Xji2 - 479.66 = 490.49- 479.66 = 10.83 MSW = SSW/N-k = 10.83/5 =2.17 F = MSB/MSW = 89.65/2.17 = 41.31 Fk-l N-k = Fl 5 = 6.61 (critical value for 95% confidence) Appendix B - 11 Rev. 3 ------- 3) 2,4-Dinitrophenol Treatment 1 Treatment 2 xi_ X2 SSI 66250 475 11.10 6.16 SS2 ND 400 ND 5.99 SS4 30000 325 10.31 5.78 SS5 30000 288 10.31 5.66 k = 2 HI = 3 n2 = 4 N = 7 SSB = (T^/ni + T22/n2) - T2/N = (1006.16/3 + 556.49/4) - 3059.20/7 = (335.39 + 139.12) - 437.03 = 474.51 - 437.03 = 37.48 MSB = SSB/k-1 = 37.48/1 = 37.48 SSW = E E Xji2 - 474.51 = 475.07 - 474.51 = 0.56 MSW = SSW/N-k = 0.56/5 =0.11 F = MSB/MSW = 37.48/0.11 = 340.73 Fk-l N-k = Fl 5 = 6-61 (critical value for 95% confidence) Appendix B - 12 Rev. 3 ------- 4) Phenol Treatment 1 Treatment 2 SSI ND 142.8 ND 4.96 SS2 138040 142.8 11.84 4.96 SS4 185640 142.8 12.13 4.96 SS5 195160 714.0 12.18 6.57 k = 2 nl = 3 n2 = 4 N = 7 SSB = (Ti2/"! + T22/n2) ~ T2/N = (1306.82/3 + 460.10/4) - 3317.76/7 = (435.61 + 115.02) - 473.97 = 550.63 - 473.97 = 76.66 MSB = SSB/k-1 = 76.66/1 = 76.66 SSW = t E Xi -j2 - 550.63 = 552.64- 550.63 = 2.01 MSW = SSW/N-k = 2.01/5 =0.40 F = MSB/MSW = 76.66/0.40 = 191.65 Fk-l N-k = Fl 5 = 6-6l (critical value for 95% confidence) Appendix B - 13 Rev. 3 ------- 5) Cyanide Treatment 1 Treatment 2 SSI 9.52 0.79 2.25 -0.24 SS2 6.38 0.83 1.85 -0.19 SS4 4.82 0.22 1.57 -1.51 SS5 1.32 0.18 0.28 -1.71 k = 2 n^ = 4 r\2 = 4 N = 8 SSB = (TiVni + T22/n2) - T2/N = (35.4/4 + 13.3/4) - 5.29/8 = (8.85 + 3.33) - 0.66 = 12.18 - 0.66 = 11.52 MSB = SSB/k-1 = 11.52/1 = 11.52 SSW = E E Xji2 - 12.18 = 16.33 - 12.18 = 4.15 MSW = SSW/N-k = 4.15/6 =0.69 F = MSB/MSW = 11.52/0.69 = 16.70 Fk-l N-k = Fl 6 = 5-99 (critical value for 95% confidence) Appendix B - 14 Rev. 3 ------- Computational Table for the F Value Constituent Benzene Aniline 2, 4-Dinitro- phenol Phenol Total Cyanides Source Between Within Between Within Between Within Between Within Between Within Sum of Squares 7.28 10.69 89.65 10.83 37.48 0.56 76.66 2.01 11.52 4.15 Degrees of Freedom 1 6 1 5 1 5 1 5 1 6 Mean Square 7.28 1.78 89.65 2.17 37.48 0.11 76.66 0.40 11.52 0.69 F 4.09 41.31* 340.73* 191.65* 16.70* * - Indicates that the calculated F value exceeds the critical value. Conclusion L/L extraction followed by steam stripping and activated carbon adsorption is more efficient at reducing the concentration of aniline, 2,4-dinitrophenol, phenol and cyanide in K103/K104 than L/L extraction followed by steam stripping alone, but is not more efficient at reducing the concentration of benzene in K103/K104 than L/L extraction followed by steam stripping alone. Appendix B - 15 Rev. 3 ------- Q W EH W H 2 £3 W H X EH EH W 2 CO W H & 2 2 W 3J P CO H H fe EH O CO 2 W 0 EH U CO 0 fo Q w CO EH EH < H W H EH tJ Q 2 2 O <3 H EH U W EH W Q U X H Q 2 W d. o, <; -a- o Q H W 4 EH rfl i-3 w K f> EH 0 H Q W EH W 0 05 H EH « 2 £3 Q W EH rt\| n W 0 tf H r . iv f ?H 2 13 EH 2 W J3 £-H H EH EH CO < 2 Q 0 CO U ^ 0) 3 c oooininotflininoiooomoooininoomtfiinininininooooooo-H OOO H OHHHOH OH OOOLOOOO-P HHH H H H d H H ^3 — CO U H 2 O O W l_3 H EH 3 O 0) 0) C £ (00) (1) a -P o) c )H O d Q) C 0) (U a) o) ^ co c a) a c C X! ft 1 (0 X! 0 0) QJQ) OJCIJ-P O CNXJ -P^Cli CTJ -HCQ) ^ I-M OJQJOjO 0)0) m-H TSnJH o oa)a)a) c -P XI ^ (0 X* ^t * — ( Q) ^6CCCVi(OJ-j Pj -p O fC -P OQ) -P-P C X!C OO(OiOQ)OftOO (C H-PH Q) rHTJ dQ) pH Q)OfO i — tV-tX3X3x3HOHin i — 1 Od)I>i g ,C-H CQ 6 > ClXtCUXJO-P-P-PXi^-lXiO >i Xl^^-i <1J O U'WOJIO H -i H(0-PWNHS-i(C4JEx!>-iB6-PI-HOOOI OI-HCCX!C-l>-lH>-(^4HQQOW'HQQQ(flQWHQf— lrHB3>i>i 4JO>iNggx)XJOx:oox!oox:i i ^cxsi i i ci ci i >,>,oxix;x; (D^-lMCOO)1-)^-! rH O ^H i^H O ^H rH O CN CN Jd (0 O ^ ^3 rH fl3 C^ (0 01 ^ XH ^H 'O O 4-^ 4-^ OOOCJ^M'0'0 C 1 ,£< C 1 i«C3 »C 1 • * "H M -r^ * ^ ^4 ^ '^ • -^ -M O W O O <3^<3fQfflCQUOUCNJOUf^OOf^HHQ^QHHH^H^OHWWHHSS Appendix C - 1 ------- Q W EH W EH 2 D W K EH EH 2 W D EH H H CO 2 O U a 0 Cn co EH H S H l_3 2 O H EH U W EH W Q U X H Q 2 H ft a. • 4J 0) o in o m 0 O H •« o o o o o o o o o in o in 0 O o o o o o o o o o in o in 0 O f~\ ^* <0 c 10 .c 4-> 0) 0 Q) ^\| Q) -C O rH -H rH •H ^ X< >H O O -P H <0 •H £ >H C U -P O 0) HO) EH >i C 0) 1 O rH -H * (0 £>iT3 c— i A S2 ^ v 4J -p 14 H Q) 0) >i - S S ft H in in 0 O o o in m o o o o in m V C (0 -P 0) o J_j O 0) ^t G f^ Q) U A (0 4J M a) -P 0 EH 0 1 rH CN £ - 0 •• M rH p v 0) ininminininino ooo rH CO f1 VO OOO oooooooo ooo oooooooo ooo lO LO l^ LO LO lO IO O O O O H in in o H H O OOO OOO OOOOOOOO OOO oooooooo ooo ininminininino ooo H m m o rH rH CO ,— ^ >J 0) X C Cn (0 P P Q) CO 0) 0) 0) C U C C fn 0 M (0 (0 O Oj 2 C C MO rfj -P -P O ^ O (1) 0 3 QJ PH Q)i-\|rHf\)X3X3fOrH 1 J3J3 ••••OO fc >"i H t— t -H rH H -H -H (N C S O ^ - - ^ Vl v-H W 0) C Q) 0) Q) H C C (0 Q) O R A C JJ 4.) d) /C .C .C p, pt p (0 (0 O C C 4-> Q) Q) Q) 000 O VO 0 0 0 0 o >m o o o o o o n 0) c a) ^i o j3 rH 4-1 o c •H B r-t > 4J o < 1 ooo ooo ooo ooo o in in n H H ooo ooo ooo ooo ooo o in in CO rH rH rH ^, C 0) x: a a) •H C .Q Q) O CD O C C 'O .,_\| .^ J_( K rH X< <-H 4J 1 C C O 000 2 n 2 H M " o ooo o ooo i< O Q O O O 202000 in in in in H r^ H i— i o ooo o ooo o ooo < 0 Q O 0 0 202000 in in in in rH t^* rH rH CO c Q) CD C X! Q) 4J 0 C (0 (U fO ^ C r< x; rH CUD P 0 JH 3 /rj r] Ql P\| U-i 1 1 ^ *^ +^ V- 1 •^* ^~^ Q) ^0 O rH ro .P •P — C 'O — ' — ' •H O fl) -H O O £ N N N N N «3 q c c c c M Q) 0) Q) 0) 0) ------- Q W EH W Oi H 2 D W rH K EH EH W 2 CO H W EH (^ 2 a w S3 »i3 co EH H Pn EH O CO 2 W Or, tH U CO & 5 0 fn Q W CO EH EH »< H W a « H EH )_} Q 2 2 0 < H EH U W EH W Q U X H Q 2 W d. < 0 Q H W tS EH rj N^ co U H Jjj <; O tx O W >_3 H EH ^ J 0 1 H Jg CO ^ Q) C OO OOOOOOOO OOO OOOO OOOOO OOO O-H cooQpirorofOMoinrOr^Mro<^XI C) CD M CNQ) Q) g4JrH4J-P-P Q) 0) <1) -MCC CO) W>iX!rH(D-H H CO) C T3CU-H -H (ucoJaJ^aj-rH -•nxt'O rHQ) >1^O Cfl-H C V-l DQJCCCC'drHrH NO-iHrH >iX! X rH M — Q) X! Q rHQ) -P (C^Q)Q)Q)Q)-HOOQ)CNNO r-l-P O^lCUrHXl-PI OrH H r^lr^r-INNNt^CC-PQJftJCCt Q) C X! Xl O ^"i f^i x! ^ Q) Q) CO (0 C X! C^i ^i C C C C Q) Q) CO Q O Q) O CLi tC O 4^ -P W ^ ^4 ^ C 4-^ O XI rH O 4-^ O^ Q) Q) Q) Q) X) XI rH ^i C Q r^ ^CQ)Q)'\|H(l)rH ^* -iH (0 h 4J O -HrH QJ •— » OOOOOXjt>-irHlrHrHOXlC& rH (0 •> -^ OOOOOOXlOG^irH •H rJCV-lV^rHrHC^irH 'H -H 1 C^l Q) O 0 rH -^ Q) -rH r^r^V-lrUr-lrU-PXifCXl^l ^ rH -fH OOO ^i Q) N ^t C N g (0 Xl r^ CO O XI w ^OOOOOO .^i -P rH 4-J XI XI ^H ^ rH rH rH X! XI C 4-^ (Ct C 1 C Pi CU CU W • (Ct (C rH rH rH rH rH rH f\ CU KI CU 4-^ «. , — . tTXlXlXl4-'&iCUdOCUOOOOCUr-ICU(0 — • • — XSXIXlXtXlXl gXlgCU tP-VOUUOCUO.QPQ^-l.QVJr-lVJj-lCOM •>— ' OOOOOOUOrH-H4J-Hg ^•— N 1 1 1 1 g 1 OOOOOOQJI O N N N> -H -H -H -rH -H -H >,Q 0) Q -H OOCCNCMtNtNOrHUHMrHHHHOlOl CCCQQQQQQXll 6 1 Q N N Q) s— • ^ s-' -' r^^iQ)X!OX!XtX!Xi^iX!'CtCUQ)Q)l 1 1 • 1 1 4J •• 'H «> 1 C CCQ 01 CO U WCQ4JCOUrHUOUU -H4-> r4£lJ3XlrrifN'<3 ------- Q W EH W EH 2 ^ W H £ c-i W 2 CO H W CO J 2 2 W CO EH H fo EH O CO 2 U OCj t~l U CO K 5 O t, Q W CO EH H W S &< H EH Q 2 2 0 < H EH U W EH W Q U X H Q 2 W < O Q H W EH ri« tfl w PH f> EH 0 H Q U EH 4 ^* w o PH H r. ^ Q W EH W 0 tf H r t kV CP HH EH 2 D EH H EH EH CO <£ 2 (0 U rT 0) C •H 4J C 0 U N— • ^~. 1^ \ &* 3 s— • CO U H >2 s o o w H EH M O [> 1 H CO ^ 0) c OOOOOOOOOOOOOOOOO OO OOO OOOOO -H ncomiTim^foncivomnfOfooinMrflQfivortjvovonrtJinininfomQ^ HHH H 22 2 2HHHH2C 0 U OOOOOOOOOOOOOOOOO OO OOO OOOOO OOOOOOOOOOOOOOOOO OO OOO OOOOO OOOOOOOOOOOOOOOOO^ n3 -PO +J(ON 0)-P 0lQO)0)(dOn3 C C Olt/lO) >i 4->rHCO>rHCCH(fl^.^ 0)0)0) 0)^ ^I-H C -P (CnJOlJ-iOOJOlnJOH-O C-Hftfl) CT3 4543 O d (04JCIO)r-IH4J4J 43 N(CH(OCai CO) -HCCQ) 1 43430)O43OO43-HO)H C -PO430)p - 0)(OC 2,'e'eC iHC 43 OOOOO H-i-lCC 43X>UO)£XD<^ 0)OHQ)OrO(OHCC-H O-i^UiWi^H>igO)a) OOOOOOiC43'HH-HO)0)rd r-H^J-H-H-H-rl-H^ OH Q<4J Q) 0 O O O 0 OH O J-IH-PH434343 ,3CCCCCO^ >i'H C CrHHHHHrH^-^ >,>,0)(da4->-P O Q) O O r Q -H -H -H pH H 0 QCQ rtJ (1) XH JM >C J^ XH ^C O W PLI X3 S -C fO .-^ ,C\| M .Q V-l ^ -P 1 Q T3 Q O Q 1 1 U) 1 MMOOOOOOC<0(0-P \ -M ^ Pi Pi-P O -P -P QJ C 1 1 1 1 ICCX! ^OO(0(0(0(Crt3tOU)W^GCT»CT>OOOOOOOOOOHHHHHHHHH HHHHHHHHHHHHHHHHHHH HfM(N(Mrs)(NfV](M(NCM HHHHHHHHHH Appendix C - 4 ------- Q W EH W PH EH 2 J^ W H SB EH EH W 2 W M M EH CU W rf! £3 W E-I H fa EH O 2 W O EH u co KjJ pj J2 0 ft, Q w CD EH EH <3 H W s « M EH t_H Q §§ H s w EH W Q U X H Q 2 < o Q rH EH K co EH 0 H Q W EH W 0 r * \/ " HH 2 ^ Q W EH < CO W 0 Pi H r, i^/* tT* ?M 2 EH 2 W J3 £H H EH Qj ff\ " vj < 2 ffl U x-s, T3 Q) 3 C •H -P C 0 CJ <-^ l_3 x^ tJ1 3 M U H 2 O PS O w l_3 H EH t-H O 1 s co OOO 2 000 OOO Q O O O 2000 in in o H H co OOO OOO OOO Q O O O 2000 in in o H H co d) C •H Q) g Q) C (0 •H g >, 0) id i — i j * T-J I-H >i (1) r— ( ^1_£3 ,— \| O 43 -P ^1 43 •4-* <1) £ Q< (D g ^J ^-1 •H -H Q) O "C 'O g g o o o o W W U) W O 0 O O i i ij i i i ,_J ,_J ,_J ,_J rn ^ T^ rn II I I III Ch 0 H CM (N CO fO CO OOO ro in vo 000 OOO OOO OOO in in o <- r~~ to OOO OOO OOO OOO OOO in in o H r- co 0) a; q a) •H T3 'H T3 -H T3 •H i— I -H ^O3 (D >-l i— 1 p, i~\| ri •H >,+J OOO W W 1 OOO Ij tj ll ,_J ,_J ,_J r^ ^l ri 1 1 1 1 1 1 co ^ in co co co 0 O 2 2 co H 0 O 0 O Q < 0 O 2200 o in in r~- H o o o o o o Q < o o 2200 o in in r- H 0) C 0) C 0) fl) C O Q -H 43 43 Q) C C^ O O O O o o o o rH rH r—f rH 43 43 43 43 (0 (tJ rtJ (0 1 1 1 1 1 1 1 \ 4-1 4-1 4- +J /ll fli nt fl\ U» U; UJ U> vo r- co w CO CO CO CO O O O O VO CO CO CO o o o o o o o o o o o o o o o o o in in in CO rH pH rH 0 0 O 0 0000 0000 0 0 0 O 0000 o in in in CO H H H 0) c •H fc C 4-* ."! "H Q) -P rH Cr-» /-» ,_j M M ™ OOO P^ fH fH H 1 ^H J-j ^H 1 0 H OJ CO ^ "i* ^* 't O O O Q co < in vo o o o o o o Q O i< O O 20200 in in o iH r** co O 00 0 00 O 00 Q O ft, 0 O 20200 in in o H r- co 0) C OJ N C 0) 42 O o ,— I X3 Q i ^ ro • -i- in vo r- oo ^}" Tj< ^t Tf "4" 0 0 2 ^ H 0 0 0 0 Q o o 200 in in H f> 0 0 o o o o Q 0 0 200 in m rH f~- rH O c 0) 0) 43 C rH a a) o ONE i^ C O o o ^^ _j Q p, ^ o o O ^-) ^ (ti O O ^_\| r-H rH 4J 43 43 QJ O O EH -H -H 1 v-t V-I VO EH EH - 1 1 ••<• in co CN ^r Ol ^ C^ 0^ O rH ^4 lO lO 0 00 co Q in co o o o 0 00 0 Q 0 0 0200 in in in H t^ rH o o o o o o o o o 0 Q 0 0 o 2 o o in in in H [» rH (U 4J fO J5 a 0 f] d ^^ rH H >i o a c o C] p, CX O O € JH O r-H O JH O i-H ,jQ ^ ^ 43 -H -H O O T3 O U •H 1 l< rH &H CO ^ EH - O 1 CN -H rH ^ '> C C r^ ^ cQ CQ CN CO * in in * * o 2 2 2 n O o Q Q Q o 2220 in H 0 o o Q Q Q 0 2220 in H 0) 0) 0) 0) C C C C 'H Q) Q) CD g N N N (0 C C C 10 Q) Q) Q) O Q O p i-i O O O -P C C C -H •H -H -H C g g g rH (0 r3 (0 >i •H -H -H C O O O O 1 1 1 r-< 1 1 1 A-i •» . ^ -rH * * * •K -K -K * 9" 0) c O -H rH C o u o o o o in [-- 0 0 0 0 o in r^ 0) C • H rH •H C fO 0 ^ H 2 1 1 f^ * HHHHH HrHHHHHH HHHH Appendix C - 5 ------- Q W EH <£ W Pi EH 2 D W rH W EH EH M 2 W H W CO iJ EH ft 2 S w Si ID co EH H &H EH ^^ CO 2 W 0 EH U CO r^3 a 5 0 ["T, Q M CO EH EH EH 0 rH X Q W EH W O Pi rH EH X 2 p Q W EH Wr- 1 ^-j « H C_i K/'* tr* PM 2 p EH 2 W EH H EH EH W < 2 O 0 ffl CJ ,-» •o 0) 3 •rH -P C 0 u »— ' ^-, i_3 ^^ tn •^* w u H 25 15 O o a H EH i_3 o i H S3 M 0 0 in n H 0 0 0 0 0 0 in in f» H O 0 0 0 0 0 00 (M/ 0 0 in in r- H Q) C r-H -v •HO J rH C X •rH Q) ET> C X! 3 ro a ^ 0 0 rH JH CO •P -P J •H -H < 22 EH 1 1 W n i 36 6 e s O -H g rH 3 -H ,-1 rH rH -H >H -H -H e c 3 rH -H e c .-H TJ •H (1) "H ^i £3 O P< T? O -V Q) ^»~t ffl O 4^ W V^ ^ O M CX fO ^ O "H rH nJ G C C ^4 (0 (D (tj XH O Q) (D >fH fl) -r^ ,Cj rtJ -rH ^ rtJ CO PQ ^i ^i ^j ^ _j 2 if^ CO 03 EH ^^ i^ ^ IO ^P ^^ CO C^ ^3 fH ^^ ^^ ^* lO ^D C1 CO IO ^^ U^ IO ^^ lO ^D ^D ^D ^D ^O VO ^D ^O ^D rHHrHHHHHHHHHHHHi-H jj O c to m J3 -P H e H rH c o H ^ i O 0) -p 0) X H ^_l -P (0 E (0 ^ 0) 5 O XJ ^ T3 0) O a) +J Q) Q P O C 01 (0 5 -P C Q) 3 •H 01 C o u 1 Q 4-1 O & (0 X) r— \| CO 2 c (0 CP c -H 01 3 •o 0) o M a) 10 to (fl Tl C 3 O g O O (U rH XJ (0 rH -H <0 ^ (0 4J o c • T3 01 O -H C •H ^ E M M (C CD "O •P C 0) i O A4 0) •H -P 10 0 > •H g 01 (0 (0 TJ 0) N >i (0 c (0 01 (Q 5 • 01 -P rrj fj C C) 3 3 O -P Qj-H € P O 01 u c 0 o O 01 -•rH i < rH ft (0 pa c - «3 5 i = E ^^ e -p (0 -H >H - CPVH 0 0) M > ft 0) ^ 01 0 C X! 0 - •H \|j /J\ 0 H •H -H r-l 4-> JJ (0 01 rH 0) O OH S rH (D (d 01 O) a10 01 -O Q 3 o T3 D< c e (0 0 J U M 01 O H <«H fi -p c (C 01 r-l -P ft 01 •H -P rH o - O r^ •n co O & V-l rH ft f"! fl) u 0 ^1 C (0 2 s- 3 H W H 01 0 E (D 01 M Q Q) rH -rH JJ (0 rH o ^ fQ 0) ,rj -P •H CD O •H Ij H Q) C (D O 0> X! P r^ •H '01 •P 0) 3 -P •H ^J 01 c o o <4H 0 4-> •H rH CD X! -p c -p c (fl •H 1 J £ (J) 3 .p •rH ^J CO c 0 0 01 •rH X! 1 * 'O - d) ^~. 4J = 01 EH H <; rH Q CQ (Q s (0 •P 6 C (0 Q) rH 3 • CTi-P CM O -H -J- €_, It . 1 M 4-1 r-l ft 01 • n o 01 O 2 c o o •H tji H •P C in O-H •H rH • M O rH J-> -P 0 01 -H > Q) C - « O rH C rt\ K w rH 4-> (0 rH 01 01 Q) -H O -P C71 (X (0 Q) 01 S Pi •H 1 Q T3 rH C (0 T3 3 rJ CO VH d) r-) C7< h rH 03 O 0 X! H X! <1> ft O tT1 r^ (0 CD it) ft 0 S C •• "" (0 H X M H H J3 O 0) 1 X 0) ^ 'H iO (D •H in a i— 1 \ i4j (0 < 3 ft C Of W -H Appendix C - 6 ------- Q W EH W Pi 2 ID w K EH H CO EH 2 U EH H EH 2 0 CJ Pi 0 CO £-1 H S H i_3 2 O H EH U W EH W Q U X H Q 2 W PH Pu W O PH H r • KJ tH PH 2 EH 2 W £-{ H EH EH CO < 2 Q 0 CQ U o o o in in OOO HHH 0 0 O 0 0 o o o o o o o o in in ooo HHH o o o o o o o o o o o o o in in ooo HHH ^~. M" \ C7* rj — • CO o H 2 a) Q) O 0) rH H rH -H O •H >-l H LJ JJ (~\| •P C -H O •H -H C OJ -H C 0) O C T3 O rH rH Q) O 4-> o >i N g 0) V-1 ^H C O O O O O M H fO -P XI 0) •P EH 0) E C e A M rtJ CQ U in in o in o H o o o o o o o o in in o in o H o o o o 0 O 0 0 in m o in o H 0) C Q) Q) -H C (0 X! Q) p 4J TJ d Q) •H CQ g 1 rH Q) C X! C •H 0) U rtJ rH Q) Q) CO -p Q) >, c a i a) (0 -P 6 x! M 6 B XI UJ M -P Q< O O •P O O Q) O ^i J-i Q) JH M-l g ^\| Q Q 0 O O O O -H -H 0 X! 0 0 X! 1 1 XI 1 X! Xl 1 ~ »• CJ fs CJ CJ ro H H in o o in in in in 0 H H 0 0 0 O O 0 0 O O O O O O O in o o in in in in O H H o o o o o o o o o o o o o o in o o in in in in O H H 0) c 0) P 0) SO) C CQ C 0) i «j x; CN Xt -P 1 P 0) O 0) Q) 0) 0) O >H g C C C JH O O (0 (0 0) O rH JH Xi Xt XI H Q) X! O -P -P 4-> X! C O 3 0) 0) 0 O Q w >H M M Q •P 1 -H O O O 1 O ^ T3 rH / — 1 i — i (N g - O X! X! X! ^ O H V-i U O O H g 1 O -H -H -H 1 O (fl rH Q Q Q 10 M C £ 1 1 1C •<-) )H -H -->•>-! 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CU 4J (0 OH CO O CO OH O CT O > -iH -H >-\| (C C • 4-» rH CU CU (0 OH W 4J O -rH 4-> U S T3WT3CO)r--HCC - - CU 'H C CU -r~i 00 4-> CU (0 (03rHHH -HT3O4JrHrHrH4J30 6 rH ft-H OH O -H W 1 X CiOE-P X!>4->WS-H cu-aowcuo coCOCOrH(OC 1C 0) (0 O C (0 O >iO Q) T34JOO(OSrHU4-)nft ioo rH-cu -H in ft C O013'~l4^COrH \ ------- Q W EH W K H 2 J3 U EH 2 H EH W £3 EH H g-i U] 2 O O o C/] EH H S3 H (J 2 O H EH U H EH W Q U X H Q 2 U D-i t^ «M 2 EH 2 W D EH H EH EH W i^< 2 Q 0 CQ U ,_^ !_} \ O1 3 • — - W U H 2 O O W (J) H EH 3 0 o o o in in 000 H H H o o o o o o o o o o o o o o o Of™> r"i i j ^ {j r-i rn O] O] (N O O O O O o o o o o o o o in in O O O O) O) in in in Q) c (0 X! -P 0) g 0) O -\| rH ^ -P X! -P C-H O •iH •(-) C Q) -H C Q) 0 C T3 0) ° CTc 0 O O O -( (0 43 >-i O 0) 4-> 4-» C rH T3 30) -H r -!-( CQ E ^ O MH Q) 1 O H Q)(BiHCr»gO)>i CM30) ». o p\| r] (C 4-) (/) N rH. ^ (^ 4-) £ f\| ^J -rH f^ \| JQ t~\ Q) }i 4JEHQOJO-H4JOO 0) £l JH "O 0) fa - gccoooooo 0'2'2°UH°U^ ^ (0 (0 •£ 1 f^ f^ \| r^ po ^i ^i rj ^o fi ri fM fi o o o in H O H H 0 0 oooo oooo CN O O O ON) 01 H oooo oooo o o o in in o in (N m 0) c a o ^_i a o ^_j o X! C C 1 XI 0) Q) r> 4J c a i o) (C O O O ^5 ^\| g g 4-1 CU O O 0) 0 ^4 M 6 i-i X2 X3 O 0 -H -H ^ iH Q Q H U M M Xl 1 * ^ U d H H m o 0 H o o 0 0 O^k t_J H O Ol 0 0 0 0 in o CN O in 0) C 0) 4-> 3 CQ 1 (N \| O J_l o r- 1 0) X! C U «3 -H XI Q 4J 1 fl) 'J' g •• O «H € 1 JS S •H i-i Q £H oinmininmininoo H 00 (N H ooooooooo oooooooooo oooooooooo CM -^ Ol oooooooooo oooooooooo oinmininmininoo inoiO]OlO]Ol(NCNOO o in rH 0) 0) C 0) C 0) Q) c 0) a c C^ jj ^ Qj ^j a> a> ex o 0)0)0)0)OCO^ ^CCCi-ilOMCU onjrtooaoo ^HXlXlXliH OrH (-1 O4J4-)4-)XI V^XJ O 30)0)fl)OftUrH Q) r-lOOO-HO-HX! T3 M-(V^^MO^-lOO 0) H •H O O O 1 O 1 -H C C "OiHrHi-HfNrHrOQ (0 (0 OXJXJX! "-X1 •> ^XJ>i J-iUOOHOHroOU O -H -H -H 1 -H 1 --H rH Q Q Q W Q UlHPr-l X! 1 1 1 C 1 C 1 1 >i •H -~ - - >-l v^-i-l >.4J QHc-ti-lE-lHEH OrHW o o o o in o •-I 01 o o o O O O O O O O^^ ^l V— ' IM^ 0 0 O 0 0 O 0 0 O o in o m oj o H a> 4-1 (0 r-f rH O ^i ,r{ k O o o (0 0) i — ( Xl C rtl 4-) (0 0) X! rH £ 4- I>i 0) 4-> rH 6 3 X?T5 0 •4J O W W H H O O H 0 O o o o o Q in 0) C 0 Q) y H >i 4J H ^ 1 1 0) g — 0) 3 C O -H 0 4-1 H C O 0 O O O O o o o in Q) 4-> (0 rH >i O (0 x; 0) g H ^! ^ Q) S Appendix C - 13 ------- Q W EH W EH 2 D W EH 2 H CO EH 2 W £3 EH H EH W 2 O U O &H CO EH H s H (_} J5 O H EH U W EH W Q U X H Q 2 ft ft HH n 0 H W EH 2 W EH H EH 2 O U 'd' Q> ^ C •H -P C 0 0 ^^ (J] \ CP 3 ^-* W U H 2 ^ O 0 (J H EH 3 O O Q 0 o Q 0 2 0 CM O Q o 2 0 0 in * 0) (0 c o H rH 0) 3 rH W -H 0) ,-1 C -P (0 H X3 C 4J 0 S > >_i rH U i l i i Q) O S S3 in o o o o o in Q) g] O 0 0 o o CO 0 o o 0 o (N 0) c •H T3 > PH in 0 0 0 o o in CM 0) d (C J3 -P 0) O J.J o rH i! o (0 ^] ^J Q) EH 04 > c— \| * • H in in in ooo ooo ooo ooo ooo in in in CM rg (N a) d (C 4J 0) O ^1 O 0) rH C £ 0) 0 X! 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X3 M rH 1 ,_\| •. >. ^\| )_l --H M EHHHEHEHHJ> co o in o o o 0 \f\ U I o o o o 0 0 f1 0) d QJ r-l (0 £ 43 a (0 d Q ------- Q W EH W EH C3 W X 55 H EH 2 ID EH H EH 55 O o Q£ o fc U3 EH H g H lJ 55 O H EH U W EH W Q O X H Q 2 W < r> W W W CU y Sj CO PL, o W EH f(, U Q W EH W Pi EH Q 2 0 P H W t£ EH W PH f) EH 0 rH * Q W EH W O PS (-1 HkX HH ID P W EH i< n W o Pi H EH « 2 D EH 2 W EH H EH EH W rfl ^ ^^ ^^ 03 U +~* T3 Q) 3 C •H -P C o U ^-* ,— . >J \ &> 3 W U H 2 0 O W ^_3 H EH M O 1 H g OO OOOOOOOO OOO OOOO ininPmininininininini4!ininini'i!inininin HH2HHrHrHrHHr>rH2<~lrHH2HHHrH OO OOOOOOOO OOO OOOO oo oooooooo ooo oooo OOPOOOOOOOOiin(o conn nororo H H rH O 0) 0) 0) C C £5 -P }H 0) (C -P n3 Q) a A JH 0) rH 43 Gi -P 0) (0 -P O 0) 43 ~43 Q) 0) >H 0) g .p H -P -P -P 0) <1> CO) W >, 43 H irHc O>-H a> r-HQ)>i^OC(0-'H C >H O rH -P O ^1 CU rH X3 -P 1 O rH 'H r4 0)C J^£SO^i(XXJ^(UQ)UliO C 43 fl, H4JO-H C <~> O O O O 0 rC J>irH IrHrHOXSCGl rH (0 ••HSCrHM^-lrHC^-irH-rH-H 1 CL\|d)O OrH -~. "• rH 'fH OOO ^1 O N ^1 C N g (d J«H rH CO O 4-H 43 ^H 3 rH rH rH 43 43 (3 -P fC C 1 C Qj C^ Q) W ^ •• — ^ O1434343-PCUQ)3O(1)OOOO<1)!HQ)(0 D^fVOOOOQJOjQCQ^43^H^JHjHCO -JH ^ — ' ^^- - N 1 1 1 Ig IOOOOOOOJ1ON OOC(NfMCNJCNOrHO,HJ-\|nHrHHrHtnO 1 C N N Q) "-' ^^ %^< "^^ M ^>i Q) X^ 0X2X3^4^ ^iX^ ffJ O fli fli i ,_j ,_j ,_j ,_j i^ii ir1! i i i r* l_i C 0) 0) j H O 0 in o rH CO O O 0 0 0 0 o o in o Hf\ " i O 0 0 O o o 0 0 o o o o r> vc 0) c <1) .rH C T> N N C C Q) Q) 43 42 O O j_i J_\| O O 1— 1 1— 1 43 43 O O •rH -rH P P I H •< n H n O rH g O O 0 P 0 2 in o o o 0 P 0 2 0 ro r-i rH O O c c Q) O rj (~! PJ di O O M rH O O rH rH 43 J3 O O •H -H P P 1 1 ^. v£) (N (N OOO in in o H H fO ooo ooo ooo ooo in in o Hi— j e\ m \ i 000 ooo 000 000 ooo ooo n n vo 0) C a) flj C N •H C T3 0) •H X) N O Q) C N -P a; i C (0 X -H £ o e P 43 (0 J3 -P H a a) >i e x! rH -H 4J >iP 0) J3 1 E 4-) •- T-4 QJ n Q P n (X o P in 2 H O o P 0 2 o in 0 0 o P 0 2 o 0 n (U C •H T3 •H H N O C C Q) 0) H a, >!rH 43 jx, •P J3 Q) -P e a) •H e P-H 1 P ^ 1 n •<* n 01 ^ Q) 3 C -P C 0 0 Appendix C - 15 ------- Q a EH w EH 2 W n K EH EH W H W EH A W § £3 CO EH H fa EH O W 2 W 0 EH U CO ^ a s o Pn Q W CO EH EH rf! H W S « H EH Q 2 2 O i EH 0 H Q W EH W 0 PS H EH * 2 P Q W EH jrf f) W 0 PS H H'v' PH 2 \|3 EH W B H EH EH W Q O pa u ^~. TJ 0) 3 C •H -p c o u ^-^ ,-^ J O* 3 •>— • to u H 55 3 CD PS O H EH O 1 H as u CO ooooooooooooooooo oo ooo ooooo rHi-(r~r-t~-HHi-iHr>t^Hi-ti-tHHi-i255Hn2f)fr)i-i2t^t^r^Hr^2 T3 0) 3 C •H 4-> C O U ooooooooooooooooo oo ooo ooooo ooooooooooooooooo oo ooo ooooo OOOOOOOOOOOOOOOOO •-lrHr-t~-t^HHHHnt^rHHHHHH H n n n H in in in in in r^ r^ t^ H r- ooooooooooooooooo oo OOOOOOOOOOOOOOOOO 00 ooooooooooooooooo oo OOOOOOOOOOOOOOOOO<;QOO OOOOOOOOOOOOOOOOO22OO ooooooooooooooooo (0 nj a) >H o Q) a O O 43 -H (1) rH 0) c •H g (0 01 0 0) G • r-f N (0 •— M H T3 (1) C 0) •H TJ (0 Q) 4J C C 0)1)0) C-H ao) 000 000 ooo < o o o 2000 O O 000 n vo vo vo o (U c •rH c (d o M o ooooo ooooo ooooo •< o o o o o Q 2 o o o o o 2 ooooo in in in co in H H <-l c-( 0) c 0) X! u I ON] 0) c •H g X! X! Q) O jC •p CU.Q i xi o o b b o rH-HCC C -P O A 0) O - 0) 3 ><-P XI V-i n 43 XI O fl) Oi CL, ^ 0) c 0) 0) >_l XI c (0 H o 0) -rH XI a) c 0) rH 0) c o c •H & 0) O <1> c •H e 10 <1) c •H E (0 a> c -H rH d) c 0 c ;>, -P 3 1 C 1 •H >i3CCCCCOM -P I Q T3 Q Q Q I I 0) C I I I I ICC •H-H - v v v v-H-H-H >i-H C (0 (0 rHHOJiuacuQJoct/ia)! - ro - i i >i>iO) (0 &-P-P O 0) O O I I •tf 2 HHHHHHHHHHHrH t-l.-lr-ti-IH.-lH Appendix C - 16 ------- Q U EH W en EH ^ W r> 5G EH EH W 2 CO H CO r3 EH CU W rij D CO EH H Fn EH O CO 2 W O EH U CO PS s o &• O W CO EH EH i< H W S (X H EH i4 Q 2 2 o <; H EH O w EH U Q U X M Q 2 QJ h^l •t O Q H W M EH (V m HH n EH 0 H Q U EH W 0 en «H H^ HH 2 p Q W EH «< M W O 05 H r , *S " HN 2 P EH 2 W g H EH Cj fA t1 WJ <: 2 f^ C^ pa u ^— ^ T) 0) C •H •P C o u ^ ,-^ i_3 \ CT ^-^ CO u H g OOO OOO Q O O O 2 o o o in in o <— ( H n OOO 000 OOO Q o o o 2ooo 000 n n vo CD C -H Q) g Q) C (0 •H g >, CU e to x! c (Q r—f ^J -H i — ( ^i U) i — t >lX! r-H O 5 IP x?cl CU g 4J M •H -H 0) O 'O t3 g 6 OOOO OOOO }-j ^4 }-\| V^ jj Jj jj Jj •H -H -H -H 1 1 1 1 i i i i OOO r- r> OOO OOO 000 OOO in in o H t^ f) OOO 000 OOO OOO 000 000 n in vo H (1) 01 C 0) C-H C •H O H t3 H O 'u 'o '5 S M tH p, Li O •H >,.p OOO 000 M ^1 M ^J Jj ^J •H -H 'H 1 1 1 111 OOO H 000 OOO Q .< O O O 22000 o in o in i-- ro H OOO OOO 000 Q <; o o o 22ooo OOO o in vo r> H 0) C 0) c (1) 0) C Q) jQ H Q) C O O N ft) >H C § 5 -H £ ,O (P C P-i OOOO O O O O -H 2 S Ic 3 "cu 0 O O O O (0 (0 (0 (ti (0 tj ij 1) Ij /-• 4- 4-1 +-* 4-1 -• rtl nt rtl rtl <~ Vy W W VU «!H OOO tO lO lO Q c~i rn rH ^ OOO OOO O O O Q o o o 2 in in in i-l H H OOO 000 000 O O O Q o o o 2 OOO co n n 0) C O Q) LI C CU 5 ^-H £ , 1 Q g (0 O O nJ Cr* -^ r^ W ^ M Q) Q) OH O f* r* 1 LJ AH in 1 M 0 00 H o o o 0 0 O O < 0 0 o 2 o o in mo H t^ CO o o o o o o o o o o < o o 0200 0 00 r> in vo H 0) C 0) N c 0) XI o LI o ,_( X! (0 M 1 \ H Q) 0 EH C 1 Q) O r-l «• C fa O t (\\ r\ \_i w \J rH * K. m /»* r>1 W (O ^ O O 0 Q o 2 o in H 0 O O Q o 2 o o r> r- 1 O C 0) 0) X! C a cu O N >-( C o o H Xt 43 2 (0 O >H rH 4~) ^H 0) O EH-H i H ^ 1 ^J" Tj" n oo f\ H o o o 0 O O 00 0 0 O Q 0 O O 2 0 in in in p" H r 0 O 0 0 O 0 o o o o o D o 0020 0 O 0 in o in H H 0) -p (0 p( (0 0 X! ^^ r-\| rH fH >i o o a ceo CU CU M rj f-{ p. p, pj p O O g O O M rH rH XI T3 O U T3 O •H -H i <; EH EH - U 1 1 CN -H lO v>0 ^^ ' O 0 0 O 0 O 0 O Q Q Q O 02220 in in H r> O 0 0 0 O 0 O Q Q Q 0 02220 O 0 r> in H cu c CU CU Q) -H C C C g N N N O O 0) 0) CU O XI ^ XI XI M O O O O 4-J U C C C -H r-( -i-l -H -H C (0 (0 (0 >i ,__! >P^ >r^ .^-j £ >i Q Q Q (D Nl i f r* 1 1 1 A-t Q) ». v «. .rH 'O 0) C O O O -M O CJ OOO OOO OOO 000 in in in r~ r- H OOO 000 OOO OOO 000 000 in in M H H C C rH •H -H O i — ( iH C •H -H Q) n c xi OOO LI ^_i ^_i •p -p -p -H -H -H 1 1 1 I I I CTiOHOrHcviro«invor^coo\O!-i(N]m * * * * * * * * HHHHHHHHHHHHHHHHHHHHHHHi-HH Appendix C - 17 ------- Q W EH W EH D W n X EH EH 2 W H W W 1-3 EH PH 2 S w 33 EH H Pn r i /"\ CH \J W 2 W O H U W « S O fn Q W W EH EH IT* PH 2 P EH W g H EH EH W Q 0 ffl U ^m^ r3 V^ U1 rj ^ rH rfj EH M S O O O O O CM O H H )• n rH O O O O O CN O H H Ti- ro H O O O O O CN O H H Tf CO H E >. 3 CO "H g 0 -H g rH 3 g C 3 rH -rH •H i g -P UJ rH rH T3 C )H (0 fl) nJ r< rtl ffl ffl O & in vo r** oo in in in in in c-H H H <-H rH O O O [•x vo in 0 0 O t^ vo in 0 0 O r^ vo m 3 g <1> O O^ 'O rH ft (0 43 O CO U U J 0"i O H in vo vo rH H H O 0 O 0 O O 0 O H O VO O VO (N CN H in H O O O 0 O O O O H O VO O VO i 3 33 ,_\| rH -H r-l -rH -rH 3 0) C 0) rH -O O X 0) > rH (0 0 rH O rH rH tS3 (fl C o u 1 p <4H 0 >1 n) ^4 j3 •H rH OQ 2 C tj> C -H to 3 TJ 0) £ O ^ n} (U U u to ^ "O c 3 O r\ g 0 o 0) i-H Q fl rH •H to > (0 JJ 0 C • O 01 OI-H c •H T3 g rH rH (C QJ T3 •P C 0) (C 13 ^ (0 c 0) 0) 0) £ XI EH 1 < 2 -P 00 -H 1 rH S W (0 CO (0 3 1 ao -o n Q) O in N •H \ >, rH < rH (U A flJ C W C Q) - tO O <— r 0) Q) EH XI J3 < EH Q >i • = g O ^ r- E -P CM 10 -H CO >H - O> rH T3 O Q) 0 rH > £! O-i (1) •P 15 0) CO O sex: o ^ >i-H 0 rH Q) -H -H rH $H .P •H 4J «J 4J W rH (0 Q) O H « > O •H (0 g w to (1) O fO (0 ft in T3 10 Q § u o (0 T3 ft C g T) ifl O Q) J O N >1 rH W rH O -H (0 '4H 43 C 4J ia c ra (A W rH .P (0 l^i 03 "3 -H •P rH W -P O - o c o r^ C H o c to O O 10 5* O IH — O Ul 3 rH v-rH U] H M 43 I/I 0 1 * o c (t3 JT rH o 0) rH •rH .p rH o > •rH g 0) w rH Q 0) rH •rH 4-> (^ (H o ^> (0 ^ 0) ^ 4J -H 0) •o ^s 4J = tfl EH-H — ' 4J E C it 0) >H 3 0 D)4J •rH O -H 0) PH tfl c c 0) W O o c o o a) -H tr> 43 -P C •P 0-H •H H C rH O •rH -p 4J W-rH W 0) C •P « 0 ^ c grHg 3 <0 rH 4-> W 0) •H O 4J -P ft tO w w > C-H 1 O Q Tf O C T3 3 +J Wll J^ rH (U -H O rH 1W Ul •H 0) C -P rH H Ot c O -P r- O CO 4J Q) en O T^l rH C 0 >H 43 •H >H a) to -PCS C C • 0) 03 H ^ M rH +J 3 o •rH 0) 1 •P W IS 0) iO O •^ fi •H in W rH \ •H (0 rfl 43 3 fc EH aw 1 * * • (M S . O 2 . H lf^ • rH o ^> .. rH •P (0 •H 17« Q) OH rH (0 rH rrj CD b 43 -P 4H 0 «. n vo vo CN 0) ^ (0 p-l •w X 1—) X •H rrj c 0) p. ft c •H Appendix C - 18 ------- Q W EH W £-1 2 £3 U ^ K EH EH W 2 CO U CO J EH PU 2 S W 5 D CO EH H Cn EH 0 CO 2 W 0 EH U CO O &H O W CO EH EH — U\ 0 — CO u M 2 < p/j 0 3 H H t-3 o ^_f 0) a) 0) 0) Q) Q) 4J C T3 -H C 0) (0 'H TJ fl rH XI ^ /rt r{ S^ -P O Q) -P P C Q) ,—1 £j P 0) H g X:-H « e > QJ O U <4-< Q) 1 O H Q) fH V4(DrtJi-HC^£Q)^i ,—1 .f-\ OC^-)^OJ -OC^ •rH ^4 rH fd 4-^ 01 N cH ^ (0 4-^ £H ^_l ^j f^ ^^ QJ 'i-^ f^ \| ^Q jc^ -(MrH>-l •PO^iNgg^XlOXlOOXiO (DMV-iCOO^-l^-l'-HUr- ii— lUiH O O O O w ^4 ^ (0 »C 1 XI .^ 1 x! f^ i^ ci pQ iV^ ^A ri rj rj f^ rj rj ^^ ri o o o in H O H H o o o o o o o o o o o in H O H H o o o o 0000 o o o in in o in -l r— 1 Q Q O XI 1 1 r_\| C_) f\j (\J X! 1 •• ^ U f> H H in o o in in in O rH H o o o o o o o o o o o o in o o in in in O H r-H o o o o o o o o o o o o in o o in in in CN O in M C 0) -P 2 0) CQ C f (Q ("^ ,£^ i -P O 0) 0) Q) Q) J-) S C C C O O (0 rtJ 0) <~t ^-i XI XI Xl fl> XI O -P -P -P C U 3 0) 0) 0) (Q H i — i OOO XI Q M-i M >-l S-l P 1 -H 0 O O O ^ 'O ' — i i~H • — 1 0 H ° U U U g 1 O -H -H -H O Ifl i— 1 Q Q Q >-( C X! 1 1 1 •H i-l -H - - ^ Q £-1 Q H H r-l ^ O P c •H inininmooooooo-p ooomooo c i ci ci i ><>iO,Qx;xi fO ^^ (0 W ^* f^ ^.C (3 O 4-J \| ^ J^ ^ V"J "'H ^ 1 ^ 4 1 Q rn Q) Qi E-lHEH OrHHWHIHSS Appendix C - 19 ------- Q W EH Ed EH 2 W M1 X EH EH Ed 2 CO H Ed EH & W 4 Ed Efi f> EH 0 Q Ed £H i^G ^J Ed 0 tf H EH ^ 55 £2 Q Ed EH Ed O tf H r_i v^ CP HM 2 EH 2 Ed ED r-t H EH E"* W -q 4J \ (0 ^ C 3 O •^ <4H a) CO rH fl) T3 O 3 rH -H H W -H k S d) V^ O < C -P rH O (0 -H 43 ttl A C U O -P 0 <1) rH (1) Ed S >i C j_^ M (1) H rH O rH EH >i a > i<3 ,£j ,rj /^ ^ -p -p -p > g s s oininminmininininino O H •* oooooooooooo oooooooooooo O H «!• oooooooooooo oooooooooooo oinintninmininininino OCNCNMCNCNCNCNCNtNC^in O (N Q) 0) 0) C C C «3 n) (C £ J3 .C -P Q) -P J-> Q) fl) 0) C Q) Q) C C E (0 O O (0 (0 O ft MM X3 £H MO O O Q) d CMMC^HMO n3(04J (OOOOJOO'O MMO) 43rHHX:CrH-H -p 4J O -P .<"! .rj -P O .rj VH OJOIM 0) U O QJ 6 O O EH EH O B -H -H O O -H rH H-HHH-iH-HtN C >i - •- Q) O M ••"•MM •••H CUHHEHEHEnHHEHEHH^* ooooooo ooo OOOOOOO O OOO ooooooo o ooo OOOOOOOi QJ X3 d -P P A .C R] (0 C C (1) (1) U U 0) c 0) o £3 iH rH (4_\| £x, 0 C 0 C Q) c -H x: o e ft C (0 -H QJ rH A £, >i 0 Q) ft-P C C O Q) -H -H -P O 6 rH Q) rtj rtj -H U 1 1 C rtj CM 'tf* KlI 0) c a) o (0 ,cj -p 0) C C (0 Q) ^-* U Q) (0 (0 -P — M -H O J3 e N -P (C C C M <1) ------- Q W EH W K EH 2 £3 W E EH 2 C/j EH 2 W J3 EH H EH CO 2 O U OH o fa CO EH H S H J 2 O M EH U W EH pa Q U X H Q 2 W ft CL. M-i •tf EH w CO s ft Jg <2 to fa o U EH CO tH £H 2 EH W D EH H EH EH W 1 a ^ •H - <~J ^ IT 0 f\\ W O (V) Q 2 o 0 0 Q o 2 o m 0 O o 0 Q o 2 0 m 0) C X! •P 0 0 P C r-H -H 4-1 ^ — •» ty ^ o »— N O C f\\ I vy 1 OQ ft -5" 0) c OOOOOOOO OOO OOOO OOOOO OOO O-H mmmmmminm^ImmmrflmmmmrtJ^ImmmvomQmmvDQm-p H2 2 22 2 2C O U OOOOOOOO OOO OOOO OOOOO 000 0 OOOOOOOO OOO OOOO OOOOO OOO O OOOOOOOO 0) (0 -P O 0) 0) Q) £ ^£ 0) 0) fc C N 0) 6-pi-l.p.p.p Q) Q) 0) -HCC W>i£H(C-H rH CO) C T3(D-H ^~ Qj & >ir-H C O ->H d) C i--^O C«J-H C ^1 OOJCCCC'C'HrH NO-HrH O>-iQj'H434J\| O>H -H Sn^iV-iNNNNlCC-PQJfCCC r"] r^ o ^t Pi f~\ vo O Q) (A (0 C f^ ft ^^ C C C C O Q) ft Q O 0) Q) 4-^ 4-J U) X CU • C -P fl) »C rH O 4-^ ft O vD Q) 0) >£H ."i rH ^i C .Q _f~\ OOO£>cHirHrHOx3C£ii H (0 ^— OOOOOOJ3O6>iiH Vl>H>-)rHC>^rH-H-H 1 CU Q) O 0«H ^-^ (D-HJ-li-l^-lS-lJ-lS-l-pJCltOXl^ OOO>iQ)N>iCNg(OX!>-i WOX3 OOOOOOs2±><-fl3(OrHrHrHrHrHi — 1 Pi tfl Vl ^ -P ,C,C,c!-PQji Q Q) Q -H CSlCMCN(NOrHOrH^rHrHHrHtOOI CCCQQQQQQXll 6IQ ^ -* ~" -* ^i^iJM'OQ) ------- Q W EH W EH 2 D W t K EH EH W 2 CO H W co K) EH CU w i H s ^ o> c OOOOOOOOOOOOOOOOO OO OOO OOOOO -H c^rou^vninrof^fOrovoinforofOr^corOi^lQfOVDrflvDvoc^rflininLrirOLOi^-p H_j ^ _j ^ i^ i-» »^ ^ _j ^ ^ »-y (-• 1 1 n 1 1 ^ ^14 ^4 ^4 1 1 I 1 f— I 1 1 ff^ )•! O 0 OOOOOOOOOOOOOOOOO OO OOO OOOOO OOOOOOOOOOOOOOOOO OO OOO OOOOO OOOOOOOOOOOOOOOOO-l CM g •PO -P(ON CD-P P^CI H C)(CO(AO)Q}n3O(0 CC 0)0)0) ^i 4JHca)HCCHW-^>-i 0)0)0) o)-^ >H-H c -P (0(Ofl)>HOfl)fl)(OOHT3 C -r-l &, 1) C"O £!A O S rH^NUCS3Xl)-i -^ 5>i Q) t3 O C (1) Q) U -PI CO)U) XI rtJ-PCIQJHH-P-P X! NiOHiOCai CO) -HCCQ) 1 jCXJQ)OX!OOX!-HO)r-l C-POXJQ)O - 0)i4-)-P-P-P4-'^il3CCCCC0^45>i-HCCiHiHi— (iHiH ,H ^^ ^(5>i5>iQ)iOCLi-P-PO(l)OO ^^-H-H-H-rH-H O Qj C Q (0 d) £ XI X3 XI Xi X2 O1- di XI S £ (OXiXl >-lX! >-l >-l •Pio'coooi i (Di ^^ooooooc^(o-pi-P2aa-PO-P-p QJCI i i i icczs -oo«j«3(0(«(0«ja)inx!a)xii ICIC-HM-H-H El^vo^-d-^oi 1 acMd3XXXXXXT(O4-)S'O4^'S22-P22 ^^ ^j P^ 5^1 ^^ ^^ ^^ ^j ^\| ^j f^ [TJ p^ JC ^C QM ^H I«C 32 HH H S^ fO "^ j^ f^ p^ f^ O^. ^r ^< py ------- Q W EH W EH 2 W •* W EH EH W 2 W W CO iJ EH CU W < »D CO EH H En EH O 2 W O EH U W <; « s 0 EM Q W CO EH EH < H W S pi H EH 1-3 Q 2 2 0 < H EH O W EH W Q 0 X H O 2 W f\^ -•• W U H 2 O Pi O W J H H $ O 1 g W O O Q n n 2 O O 0 O Q 0 O 200 0 O 01 n 0 O o o 0 O Q 0 O 200 0 O 01 01 0) C •H 0) € C -H r- 1 -H g >i S (0 X5 i— 1 >-i <1) ^i £* • — 1 x; v >i •P 0) XI 0) 6 -P •H -H 0) 'O O 6 OOO {/) U3 U3 OOO J^ J_j ^ i) I j i i .,-j >P^ .,-j I I I iii o o VO 01 o o O 0 0 0 0 0 0 O VO O o o o o o o o o o o O 0 VD fO 0) 0) C C 1— ( TJ O >~1 J* >-( P, Q) &•! Oj 0-H o o W 01 o o J--J M I) 1) •H H 1 1 1 1 O 0 in vo (—( o o o o o o O 0 O 0 m vo H o o o o o o o o o o o o in vo H 0) C 0) -H C •H "O rH •(-( O 3 }-4 rH >-l O >1-p o o o o M M •P -p .—1 ,_J rn «n 1 1 1 1 y in o Q rtj O 2 2 01 o 0 Q < 0 220 o o 01 0 0 0 Q < 0 220 0 0 01 0) C 0) N C 0) 0) C Q) _O rtj C O N (0 M C X3 -P Q) 1 J rH X5 OJ C 000 OOO X3 X3 X< OOO (0 (0 (Q J_> _D Jj T^ -r^ -r fll m n\ \V W Mr/ OOO in vo 01 (—i OOO OOO 000 000 OOO in vo 01 H OOO OOO OOO OOO OOO OOO in vo n H r-l o £ 0) rj O) Q) O C O -H Vl £2 0) -P O O C (0 (0 (0 i i I-" r* +* »-< ^ C 0) 0) fll f-l (-t VU >H 4-i O O O O 01 01 Q 01 4J m xi a 0 r\| p. ^-v H >H >1 o a c o £ a O EH >-( O O M rH XI O X) -H -H O T3 O -H i <; EH «• O 1 CM •<-! CN EH PQ o Q Q Q If) 2 2 2 rH O 0 Q Q Q 0 2220 0 in rH o o o Q Q Q 0 2220 o in H 0) 0) 0) C C C 0) 0> 0) N N N C C C 0) rQ jQ Q -iH O O O rH C C C -H •H -H -H C (0 (0 (0 O •H -H -H ^ Q Q Q -p i i i .^ iii "i _ w ^ i ^ ^- ^ i -P C 0 U HHHHHH HHHHHHHHHH Appendix C - 23 ------- Q W g-i K]J W PH EH 2 £> W ^ X EH EH W 2 CO H CO J EH ft 2 S w <2 £D co £H H Pn C, x-s tH V_J CO 2 W O EH O CO ^ a s o pLj Q w CO EH EH "l! H W £ K H EH Q 2 2 O C" »-H 2 D EH 2 H H EH EH CO < 2 Q 0 CQ U ^^ •a QJ C -H •P C 0 V— ' .-^ l_3 \ CT1 d co U H 2 <; O a o w i_3 H EH rH O 1 H s CO o o rH " O 0 O O Of-\ ^f 0 0 0 0 in r> H 0 0 O 0 O 0 Ort v_^ o o O 0 in n rH QJ c: H ^ •HO h-3 rH C \ •iH QJ U> C X5 d (d CX ~ o o >H r< CO -P -P r3 •H -H <\| 22 EH 1 1 W r> H id i d d d rH d -H >H r< H -H M --H -H rH-Hgd) dQJCQJHT3 ^i K O QJ TJ O ^^ 0) ^ ^™H ^3 O W ^3 W Oi (tj w O (™H ^™ ^ (0 C C OJ(dX!OQ)Q>-HN r^ oo ^^ ^D rH ^^ ro ^* 10 ^D r^ co ^^ ^^ lO ^D y3 ^D ^D ^D ^J ^D ^D ^D HHHHrHrHi-HHHHHH 4J O C CO (0 .p H g H rH c o H 4-> O QJ -P Q) T^ W X H ^ -P (d g to - ^ QJ rti w 0 •h. •a 0) •P u 0) -p QJ Q •P O c U] (0 5 -p c 0) 3 -P 'rH •P [fl C o (J 1 Q 2 <4H 0 & •< o rM Q) •H 4J fl3 o > •H g Q) U rrt (U CO t3 Q) ^ rH id c Q) in N X >i ft a Pa c - (d P Q) EH XJ <: Q >i ff\ —i W IQ V— ' g P id -H rj ^> CT1 r4 O QJ r< ^ ft QJ CO O C X5 O - •H i i /i) •t-1 w U rH -H -H M 4J -P id CQ H O O PC > rH Id H H ft r{ QJ U D V-i c H - d rH CO H CQ O 33 1 O •H I . W c OJ o Q) XJ •p c •H CQ -P C 0) -p •H jj CQ C O 0 •rH U C CT^ O J^ O +J Q) -H H H .H -P 0) id ."! rH P O •H O g QJ P CO O C H O CQ •H Q) rH P •1— i f^ P Q) (0 3 rH P O -H ^ P CQ id c 0 ^ U QJ X3 CO •P -H -H £ QJ EH 1 * * T3 - QJ P CO EH-H Q CQ CO = id p g c (d QJ CT1 -P (N 0 -H •<* 1_1 1 1 i H 4J cH C 0 W O 2 C U O •H CJiH p c in U -H •H r4 • >H O rH P -P O CO -rH > QJ C - « O r4 efll ty rH P (0 rt U) CQ Q) -H o P tr W ££ PH Q T3 H C (0 T3 3 k fO J-i (D t_3 tj\ ^ ii yr« /i\ rH (U U; 0 A tH CQ P C MH id P o rH H ft - • ^i P r^ ro U CO VD QJ <7i «3 •n H O] O r-i x: o) ft O CP r< (0 QJ id ft o s C •* " id H x ^4 r— ) }_\| d o CO 1 X CO 3? H iO Q) P ro Oj •H in ex H \ "C id < d ft c O W 'H Appendix C - 24 ------- Q W EH W EH 2 ID w in E EH EH W 2 CO H W CO J EH 0* W rfj !D CO E~* H Cn EH O CO 2 W 0 EH U CO (X S 0 Pn Q W CO EH EH < H PL) S K M H J Q 2 2 O EH 0 H Q W EH W 0 « H HKj/ HH 2 Q W EH 4 n W o « H r . v> tH HH & EH 2 W CH] H EH EH W < 2 Q O « U oooinmoinininoinoomoooin OOO H O HH HOH rH H H H H oooooooooooooooooo ooominoinininoinooinoooin ooocNojinfviPjfNOfMinincNinoinr^ in in in in in oooooooooooooooooo oooooooooooooooooo oooininoinminoinoomoooin ooocN-l (0 XH >1 rH (1) U .poOJ-P-PC XJC M c i xi < 0) O O-((0-Pgj^(-lgg ^4 4-^ X« Xl O *H! C 1 .0 x! QJ w \| ^ fx o O ["T"] ^J fJJ >p^ Q ^J ^_\| Q QJ Q >r^ ^J O O Q) O ^ ^-1 hH "M "H C Q) '"H O »Q JH C O M M g M Q Q M CQJOC'OgCCOOOOOOOO-H-H £-1 OrHrH(DOOOOVlrH>-l>-\|r-H>q^\|rHQQ ^ 4JO>iNggXlX>Ox!OOX!OOX!l 1 ^D O O U ^ ^ V^ ^ /O j2 1 ^ j^ I ^2 ^ I ^ ^ ^^ (^ rt3 i^ rn o3 cQ CJ CJ CJ ^^ CJ CJ ^^ CJ CJ co f"H nH in o 0 H O O in o CNJ O in 0 0 0 0 in o CN O in 0) C 0) -P 3 pa i i o J_j o r— f Q) J^ C O (0 -H Xl Q •P 1 0) ^* g * O ^H g 1 V-t C Xl <0 •H >-l Q EH oininininminm H oooooooo oininininminm lOcNr^fsjcNCijcNrv) oooooooo oooooooo oininminininin inCNJC^JCNJCMNOJCNl 0) o> C 0) C 0) Q) C Q) tt C 1 Q) Xl rH Q) S O O S -P ^i •H Q) 4J rH rH Q rH rH g 3 >-l >-i 1 >i >, O X! XI X! - -p -p O Ul ------- Q W EH « EH 55 w in K EH EH W 55 CO H CO tJ EH 0. W I? O CO EH H tn EH O CO 55 W O EH U CO « 2 o Pn Q W CO E-" EH •< H W S 0^ H EH Q 55 55 O ff> H EH U U EH W Q U X H Q 55 U (X CO u H O o 3 H EH \|j\| O CU CU * c c Q) (0 (0 -p x: x: (C -P -P c cu cu o o o 4-4 (\|) MM rH 1 C CU 1 I rH rHOrH-H --OC ^i 10 J^i'OHOJ (C Q] X5 X5 X3 "H — — M 3 •P-P4-) MHH^Jr- d) CO CD >i - -CUO SSJSP^'-l'-IEHEH inininininmo ooooooo o ooo H COCOlOVOVOCOCOiococo co incoco H OOOOOOO O OOO OOOOOOO O OOO OOOOOOO OOOOOOO O OOO OOOOOOO OOOOOOOJ 5) \ c o^ 1C 3 f* ^— ' 4J 0) CO 0) CU Q) C CJ C C B « H (Q 1C O ft «5 X3 X3 M O rtj •P -P O M O 0) 0) 3 ft « CU O O 0) H O O C M M C XJ--OO->i H M--MM--H M EHHi-HEHEHH> CO 0) C 0) Q) C M Q) Q) 0 C XJ 3 CU -P rH rH O C CU , «J CO (0 C O C M CM OJCUCUCa) X3H Q)O rHCC-rlXJ -PO M3 fCOOgft Q) C-H >irH X!X:CCO-H c ccxjoft1-! 4J -P 0) rH X) CU -s.pC~~ x:x:x:>iOcucu<:<-H.p ------- Q W EH H EH 2 ID W ac EH 2 H W EH 2 W £3 EH H EH 52 O U P o Pn W EH H 2 H ^ 5; O H EH O W EH U Q U X M Q 2 U IX < m EH W CO H t_4 0-1 Jg 3 W Cn 0 W EH CO fcH Ht4 J3 EH D EH H EH EH CO < 2 Q O CQ u _. T3 0) C •H -P C O U — ^ ij v^ C7> 3 •»-' CO U H 52; H -P (U C (X (C — 0 •H ;3 -iH "^^ ET> y <~^ ^ O O N N C C m n\ w w CQ CQ OOOOOOOO OOO OOOO QnnnnnnioortJnnnrtjMcinn 2 H a 2 oooooooo ooo oooo oooooooo ooo oooo QOOOOOOOO( O a) x; ^x; a) Q) M E4->rH4J4J4J 0) ft) W>lX!r-l(0-H H C — . a, a >irH c QJ-H a) >r-^OC(0-H C>H O t i-H \ 1 ,~^ fl) f^ Q i-H fl) i i (^ O ^l Ql rH Xi -P 1 OrH -r-( }-\| Xl X! O ^i Pi x! ^ 0) 0) W (0 C X* Q) 4-^ \| ^ CO X 0[ ^ £ 43 Q) C] I-H Q ^J C CD 0) "'H Q) i-H ^* 'H (0 ^) 4-J O '~l C C^^^HlHC^irH-r-l-r-ll dl Q) O OiH ^~- >r^ OOO ^i CU N ^i C N £H fl3 ,^i ^ CQ O Xl O^ X! Xi XI 4-^ 0\| O^OQ)OOOOCUMO(^ OUUUCUOXtCQMXtM}H)HMCU^-l — * N 1 1 1 1 g lOOOOOOOJIUN CtNCNJCMOJOHOH^rHrHrHrHlOO 1 C d) ^ -^ — ' - ^ ^i(DXl OXlXlXlXl ^i XI 0 fl) CQ CO 01 03 lOCQ4-COUi— lOUOU J-(4-> inXl 1 ^ »-^ r^ ^ 1^1 \|C-I 1 1 l(-LlfTl -r-l I rn n f^ n \| ^j i i ^^ till ,J^ M iw ™ PuCQCQCQCQ^tCQcN dU ftCNCMnUO Pf O 0 2 2 O o < < 0 220 o n O o o < < 0 220 0 n Q) C Q) 0) 0) C C ^ d) 0} >1 J-J N P^ !>i C P-I d) "^^. 0 O VO fl 0) c r"1 O N N C C C Q) fl) fl) .f"! 000 M M M ooo XI X! X! U U U -H -H -H Q Q Q 1 * 1 H m iQ CD xi i e Q) co Q Q n CX — . 01 D C O -H Q ro 4-J 2 C O U o o Q 0 2 0 0 r> 0 0 0 Q o 2 o o n 0) C -H T5 •H i— 1 N O C C o o Xt XI >1H X! ^i 4-> XI 6 "Q) •H 6 Q-H 1 Q «. 1 fi 'd* n ------- Q W EH i EH 2 "") w in K EH EH W 2 W H H CO tJ EH Oi W § ED co EH J_j pT EH O CO 2 U 0 EH U CO rtj a s o PL Q W CO EH EH < H W S & H EH Q 2 2 0 < H EH U W EH Q U X H Q 2 W QJ HH 0 Q H W !S EH fcH PQ 2 £3 Q U EH i \ H Sj CO •5" Q) c OOOOOOOOOOOOOOOOO OO OOO OOOOO -H nnHHHMnMn^HMnnnnr02201V02VOVDr°2HHHriH2C O C^ OOOOOOOOOOOOOOOOO 00 OOO OOOOO OOOOOOOOOOOOOOOOO 00 OOO OOOOO OOOOOOOOOOOOOOOOOrt;QOOiid)^ (0 •PO 4J(ON CD-P PnCI ' — 1 ojflcuwcuaiflota c c cuiacu >i 4->HCO)HCCHW^>H fl)Q)0> Q)^ M-H C -P (OfCd)MOQ)Q}fOO rH T3 C rH P) d) (^ 'O J-3 Q O i3 rH x3 N O C ^J H3 X-! M N— »^i (U O O C 0) fl) O 4^ 1 C Q) d) »Q (04JCICUHH4J-P x: ^a«Jr^(OCal CO) -HCCQ) I X3X!ClJO£:OOX5-HO)rH C+JOXiClJO- 0)(OC 3-H-HC HC •PQiJSI&i+J-PtliCC^Cl) CDjSJ^-PjG^-in CHCU cTfiiS'HCUOl 43 OOOOO H-HCC ,Q,QOC1>Qt(1)',H'n.e1S£ 'i'bl c * ^ 'o rH4J-H-H-H-rH-H4-> OH tt-P 4) O 0 O 0 O OH 0 MH4JrHX3X3X! «3 C CXW >l\|3CCCCCOiH >i-H C CrHrHrHHHrH-'}-! >i>ir^ .f-f 0 CXCQ (d Of^HrCf^f^HfJiH^H OH-I CUpJ^g^ (0 <"] f^ ^-\| Q i-J Lj -P 1 Q T3 Q Q Q 1 1 (HI >-iV-iOUOUUUC'0(C-PI-P2CXDj-PO-P-P OCI 1 1 1 ICCrH M -H H eiTj-vot-tvoi 1 afN33XXXXXX'dO4->S<ft'»'222-P22 Cj Ci ^H ^ ^^ ^^ ^^ ^^ ^^ ^^ ^^ ^y_j ^^ JC ^^ t£ tC t£ ^C HH H SMI ro ^* \|Z i^ rH ^^ Oj v^ ^J* r^\ CTi mOiOOOOOOOOOOH HHHHHHHHHHH HHHHHH HHHHHHHHHHH Appendix C - 28 ------- Q W E- W 5^ 2 £3 W as EH 2 H CO EH 2 W ID EH H EH cc 2 O U tt o PH CO EH H £ r- 2 O H s H EH U Q U X H Q 2 < in EH H CO 3 (li £ "5 co fH O U EH CO ^4 5 Q W EH W « EH Q 2 < o Q H H tt EH rfj t£ W Pi f> EH 0 * a u EH < -4 W O Pi H r . K-* C1 HH D Q W EH < n W 0 Pi H p . kv t^ ?H ID EH W D EH H EH < 2 03 U ,-» •0 0) C •H .jj C o u ,_» r3 o^ £ CO U H p* H OOOOOO OOOO oooooo oooo QOOOOOOQ« r> \o ro in o o in vo o rH CO rH OOOOOO OOOO oooooo oooo oooooo oooo QOOOOOOQ, 0> 4) C 0> C (0 i~H -M ^H ••H T3 "^ C Q) »Q f^ i~H ^i O r~H 'O ^ T3 fl) C O O ^i «£H i™ H 0 >rH i™i *H N tJ V^ C r\| ^j ^^J M O ^ C X3 4- flJ aJ Q 2 O O O O 0 O Q 002 O O 0 O 0 0 o o 0 O Q 002 0 O n o 0) C 0) •H T3 >~H 0 € O U (0 C._j r* "^ M i-1 I l_i 4-i 1 W O O p"> ft, in 2 H 0 0 0 0 0 i< 0 020 0 0 n in H 0 0 0 0 O 0 o «< o 020 O 0 n in H f~\ 0 •H €) Q) O <~™l C M O rti rt LJ vy w r-( s. fli /rt r'l U/ IU pLj P^ C/3 o o VO Q CO 2 o o O 0 O Q 0 020 0 0 VO f") o o O 0 O 0 O Q O 020 0 O vo n C H a) o N C C Q) 0) JQ a Q) DON OOO) r-H rH ^3 4^ J5 O o u ^ (0 (0 O ^_) J^ r_f jj 4J f^ 0) CO O EH EH-H in vo EH V ^ 1 ^> Tj- Tjl CM n M H (N rH O O in fi H 0 0 O 0 O 0 0 0 o o in n rH 0 O 0 0 o o o o 0 O 0 O in n H O O c c Jfl A O< & O O ^-J ^J o o rH r~t A & U O •r-t -H EH EH 1 \| in vo • • CM CM 0 O Q m f> 2 H 0 0 0 0 Q o o 2oo 0 0 in n H 0 0 0 0 O 0 Q O 0 200 0 0 in n H 0) 4-1 (0 XI a Ul o a ^~ rH a o J_l Gi o g O rH >-i O C\ f^ f^ ••H -H O T3 O O 1 < rH • o CM rH rH - O ^"i WIM IO CM CM Lj fll fll ri vy w Q 2 Q 2 Q 2 0) C CD CO C Q) Q o C •H (0 •H Q \| 1 H" O 0 Q Q in in 2 2 H H 0 0 0 O Q Q 0 O 2200 o o H rH O 0 O 0 O 0 Q Q O 0 2200 0 0 in m H H 0) c 0) Q) -H c c e i O H H C M Q Q 0) -P 1 I r4 -i-J 1 1 >i-4 ~ fc, fc..-J 1 • ^ ~ 1 TJ 0) 3 •H -P C o u c^OHCMco'invot>-coa>OH(Nn'j'invor»oocTiOHr>]n* * * * * * * HHHHrHHHHHHHHHHHHrHHHrHHHHHrH Appendix C - 29 ------- Q W EH 3 0^ EH £} H E EH 53 H CO 55 U g H CO 55 O u « o fa CO EH H S H J 55 O H EH U EH Q U X H Q 2 W ft ft in EH W CO U 1— ) ft £ 1^ CO &•! u H CO ^j 3 Q W EH W EH Q 2 ^» o Q rH W M EH OH n EH 0 H W Q M EH rfj T^ Wo ^^ « H r . l^t fcH PH P Q H EH < n Wo ^— ' « H r . ^> 2 £D EH 2 W EH H EH EH CO < 2 Q O ffl U ^ T3 0) 3 C •H 4J e o u •^^ ^, ij N^ tJI 3 CO U H § O o u l_3 H EH a o 1 H s M 0 tn U I H O 0 O 0 in rH 0 0 o o o in rH 0) c •rH rH •H C O $ •H 2 1 en * * o CO O O o o i § g g g g C 0 -H g 3 >i3 33 O -H g H 3 -H k ^ H -H >H -H -H gC3rH-HgO) 3 0> C Q) rH -O •H 0) -H >, g O O«TJ O X <1) > rH flj O <<05CQUUUr3g2cotOE-<>N -tmvop-cocOrHcNn<tnv0r-co inmminininvotovovovovoiovovo HHrHHHHHHHrHrHHHrHH 4J O C 01 (0 £ p H g rH H B O •P O (U -P 0) •n w X •H rH -P (0 g (11 w s 0 J^ *. T3 0) 4J D (1) 4J 0) Q •P O C to fO > 4.j (5 CD 3 4.J •H 4.^ W e u i Q 2	e •H u 3 T3 0) ^-i O (0 0) (0 10 (0 £ 'O e 0 0 o •» 0) rH XI (C rH •H (0 ^J o e T^ W 0) -H c g T< M (0 0) T3 •P C CD «3 'O -P in c 0) 0) X> EH , 2 4-> CO •H 1 rH 2 UJ (0 CO (0 3 1 O o T3 n Q) O in N -H \>, Q) ft 0} c w c 0) - It! O — s Q) 0) EH XJ EH Q >i M/H •u o ^ ps. g 4J CN (0 -H CO r< * CT1 M •O 0 Q) 0 r< > XI ft 0) •P 3B QJ W O O - ^iH n j_) rti 4J -4- w O rH 0) -H -H rH rH -P •H 4J «5 •P W r- 1 (0 Q) O rH « > 0 > rH (0 •H (0 g CO CO (o a W 73 /rt -•-! r* I(J "rn j^, Q 3 (0 O (0 T) a c g 0) rl 0 N ^•t )H CO rH O -H XJ P C •H U) 4J 0) p •rH -P 0) c o o •H O c (d (M E10 O -P Q) -H r-H H -H •P Q) (rj ^J rH -P 0 •H O g 03 O C ^1 o w -H 0) rH I * •rH {^ •P 0) (Q \|3 j j \ O-H r* -P U] n3 C O rH U CD XJ 03 -p-H Q) EH 1 * ro - 0) '--•P r 01 EH-H Q CQ 01 s (0 ^J g C (0 (1) tr>-P CM o -H ^ i . i * i rH 4-* rn ft 01 • c o c 8 ^ o •H U>H •P C in O"H r< O H 4J -P O 01 "H > 0) C - K O rH (= n) E5 w H 4J (0 rH CO 01 Q) -H O -P tT a (0 H (0 Q) (0 ft 0 S C v ** (0 rH X 01 1 X iO 0) •P n n •H in a rH \ rtl ro < a w -H Appendix C - 30 ------- APPENDIX 0 Calculation of Treatment Standards Constituent: Benzene Effluent 1 Sample Set Concentration (mg/l) 1 0.042 2 0.005 4 0.019 5 0.011 1 Percent 2 Recovery 76 76 76 76 Accuracy 3 Correction Factor 1.32 1.32 1.32 1.32 x = Corrected Concentration (tng/l) 0.055 0.007 0.025 0.015 0.026 4 Log 5 Transform -2.900 -4.962 -3.689 -4.200 y = -3.938 s = 0.867 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-12. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-3.938 + 2.33(0.867)) = exp (-1.918) = 0.147 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 01147 / 0.026 = 5.654 Treatment Standard = Corrected Effluent Mean X VF = 0.026 X 5.654 = 0.147 mg/l Appendix D - 1 ------- APPENDIX D Calculation of Treatment Standards Constituent: Aniline Effluent 1 Sample Set Concentration (mg/l) 1 0.030 2 0.030 4 0.030 5 0.960 I Percent 2 Recovery 91 91 91 91 Accuracy 3 Correction Factor 1.10 1.10 1.10 1.10 X Corrected 4 Concentration (mg/l) 0.033 0.033 0.033 1.056 0.289 y s Log 5 Transform -3.411 -3.411 -3.411 0.054 = -2.545 = 1.733 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, tn, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y +• 2.33s) where y = the mean of the tog transforms s = the standard deviation of the log transforms. Therefore, C = exp (-2.545 + 2.33(1.733)) = exp (1.493) = 4.450 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF - C / x = 4.450 / 0.289 = 15.398 Treatment Standard = Corrected Effluent Mean X VF = 0.289 X 15.398 = 4.450 mg/l Appendix D - 2 ------- APPENDIX D Calculation of Treatment Standards Constituent: 2,4-Dinitrophenol Sample Set 1 2 4 5 Effluent 1 Concentration (ing/ 1) 0.380 0.320 0.260 0.230 Percent Recovery 80 80 80 80 Accuracy 3 2* Correction Factor 1.25 1.25 1.25 1.25 Corrected 4 Concentration (mg/l) 0.475 0.400 0.325 0.288 Log 5 Transform -0.744 -0.916 -1.124 -1.245 X = 0.372 y = -1.007 s = 0.222 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. * - Average of Percent Recovery for Semivolatiles with greater than or equal to 20% recovery as listed in Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the tog transforms. Therefore, C = exp (-1.007 + 2.33(0.222)) = exp (-0.490) = 0.613 and VF = C / x . 99 where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 0.613 / 0.372 = 1.648 Treatment Standard = Corrected Effluent Mean X VF = 0.372 X 1.648 = 0.613 mg/l Appendix D - 3 ------- APPENDIX D Calculation of Treatment Standards Constituent: Nitrobenzene Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.03 0.03 0.03 0.03 115 115 115 115 0.87 0.87 0.87 0.87 0.026 0.026 0.026 0.026 -3.650 -3.650 -3.650 -3.650 0.026 y = s = -3.650 0.000 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-3.650 + 2.33(0)) = exp (-3.650) = 0.026 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 0?026 / 0.026 = 1 A variability factor of one was not used in calculating the treatment standards. The variability factor of 2.80 was substituted for the value 1. VF = 2.80 Treatment Standard = Corrected Effluent Mean X VF = 0.026 X 2.80 = 0.073 mg/l Appendix D - 4 ------- APPENDIX D Calculation of Treatment Standards Constituent: Phenol Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.030 0.030 0.030 0.150 21 21 21 21 4.76 4.76 4.76 4.76 0.143 0.143 0.143 0.714 -1.945 -1.945 -1.945 -0.337 0.286 y = s = -1.543 0.804 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm. In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): coo = exp (y + 2-33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-1.543 + 2.33(0.804)) = exp (0.330) = 1.391 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 1?391 / 0.286 = 4.864 Treatment Standard = Corrected Effluent Mean X VF = 0.286 X 4.864 = 1.391 mg/l Appendix D - 5 ------- APPENDIX D Calculation of Treatment Standards Constituent: Total Cyanides Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.565 0.597 0.156 0.129 72 72 72 72 1.39 1.39 1.39 1.39 0.785 0.830 0.217 0.179 -0.242 -0.186 -1.528 -1.720 0.503 y = s = -0.919 0.818 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-14. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): GO, = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-0.919 + 2.33(0.818)) = exp (0.987) = 2.683 and VF = C / x 99 where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 2?683 / 0.503 = 5.334 Treatment Standard = Corrected Effluent Mean X VF = 0.503 X 5.334 = 2.683 mg/l Appendix D - 6 ------- APPENDIX E - ANALYTICAL QA/QC The analytical methods used for analysis of the regulated constituents identified in Section 5 are listed in Table E-l. SW-846 methods (EPA's Test Methods for Evaluating Solid Waste; Physical/Chemical Methods. SW-846. Third Edition, November 1986) are used in most cases for determining total waste concentrations. Deviations from SW-846 methods required to analyze the sample matrix are listed in Table E-2. These deviations are approved methods for determining constituent concentrations. SW-846 also allows for the use of alternative or equivalent procedures or equipment; these are described in Tables E-3 through E-5. These alternatives or equivalents included use of alternative sample preparation methods and/or use of different extraction techniques to reduce sample matrix interferences. The accuracy determination for a constituent is based on the matrix spike recovery values. Table E-6 present the matrix spike recovery values for total waste concentrations of benzene, aniline, nitrobenzene, and phenol for K103/K104 and for total cyanides for K104 for the EPA-collected data. Because 2,4-dinitrophenol matrix spike recoveries were not collected, the V- average of the percent recoveries equal to or greater than 20% for all semivolatiles was used as the percent recovery for 2,4-dinitrophenol. Appendix E-l ------- The accuracy correction factors for the regulated constituents for the treatment residuals are presented in Table E-6. The accuracy correction factors were determined in accordance with the general methodology presented in the Introduction. For example, for benzene, actual spike recovery data were obtained for analysis of liquid matrices and the lowest percent recovery value was used to calculate the accuracy correction factor. An example of the calculation of the corrected concentration value for benzene is shown below. Analytical Correction Corrected Value % Recovery Factor Value 0.042 mg/1 76 100 = 1.32 1.32 X 0.042 = 0.055 mg/1 76 Appendix E - 2 ------- Table E-1 Analytical Methods for Regulated Constituents Regulated Constituent Analytical Method Method Number Volatiles Benzene Purge and Trap 5030 Gas Chromatography/Mass 8240 Spectrometry for Volatile Organics Semivolatiles AniIine 2,4-Dinitrophenol Nitrobenzene Phenol Continuous Liquid/Liquid 3520 Extraction Gas Chromatography/Mass 8270 Spectrometry Column Technique Inorganics Cyanides Total and Amenable Cyanides 9012 a - Environmental Protection Agency. 1986. Test Methods for Evaluating Solid Waste. Third Edition. U. S. EPA. Office of Solid Waste and Emergency Response. November 1986. Appendix E - 3 ------- to •f) 3 c_ « g ID U n 1M UJ 3 in >— for dev lat ion _oj "i o •0 QC CO S 3 o o s 1 T 5 T3 O 0) Z (/) ~ 5 ll \| ? o c - J = 1 1 If Ms O 3 irt •— "° ** 1 ' 2 0 S - 0 " > g 2 > S ifl 4) > "O O O CgOJO/ ft) O 0 Q> O (U ' — t— C — Q. 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Q) 5 »•-* E 3 --"•— E •— <0 QJ QJ 4->3««- QJ X E ' — O (/) U U ™ — ~ CT O F" f— 3 'OQJCl-QJQ.l- "D UJ <-A h— QC O — C 1- O C 5 TJ E x >^ — E « 3 t- U 4^ >, (rt — "D -O 3 3 O E QJ 03 QJ O QJ L. O> I- 3 «O Q. (TJ QJ U i O3 OJOJ 3Q.QJ ^OQ t-CX. JE<- 3(JU 3E "3QJ3 O-- l- Q. QJ u. QJ (rt J QJC ECOJ 6- cc QJ <— QJ O W r~ QJ (J O O QJ O U- u J 3 03 0Ct- QJQ.U JZJZ'^ O "* CWO C ------- Table E-5 Specific Procedures or Equipment Used for Analysis of Cyanides When Alternatives or Equivalents are Allowed in the SW-846 Methods8 Analysis SU-846 Sample Alternatives or Equivalent Method Aliquot Allowed by SW-846 Methods Specific Procedures Used Total and amenable cyanide 9012 500 ml Hydrogen sulfide treatment may be required. Hydrogen sulfide treatment was not required. A Fisher-Mulligan absorber or equivalent should be used. A Vheaton Distilling Apparatus absorber was used. a - Onsite Engineering Report of Treatment Technology Performance for E. I. duPont de Nemours, Inc., Beaumont, Texas. Table 7-6. Appendix E - 10 ------- 3 at 4-o CA to 2 ra i_ i— c_ o W 41 • ^ O o u 0 CX '5. to X C- z ~? UJ 41 2 <0 X « u * a e. lo O 3 4- U U 0 CO < u. * 4) 4^ a o S 0 41 4> C/> 4-* X I t u > t_ o 41 O a S ^ (A 'S 41 -1 41 5 H ^ 'o. 5 j < 5 41 ^ 'a 4-* 41 V) 4> (/I 4- V c c 41 41 U > 1. O 41 U " ~ CA ^^ 41 -1 41 D 's- s O —1 41 5 .. 4J s 1 1 2 u. <^ o 4J 4J (A 8 U t— I CM O in K. ^O O ro «- rg «o N. M «- «-^ «-" o N* «-^ •s* f O in O O O O CO i CM in i o g ; g g , NO N. m NO •- N» C^ 00 «^" CM «O ^ ' IM K> in O i K» O v- " 8 O O i O O in o i o o o 0 • 411 41 CD C - •— £ — O — 1 o\| com o N ^rc^ i V 4-> — ID 4- > O C "o S .— a -4- E 41 «- £ u I (A f r- fo 4-> i. o 5 g 5 «J- <\J 41 N. C S 41 "O 4. « .£ 2 x »- a « 1 t ° S ? W > 4> « O Z 0 01 C O CO (0 H •S J! O 4) 4) O) » a. o j: 3 i- 3 — • > 4^ 41 Q. Ul 4t O O xx t • -c u to if\ a L. o 4J 41 4) g 41 .3 S - & «. I =: - Q 0» C- O 4- t- E -c o c- E co 01 5 - H- 4-< S — a. •— c. o * ? Si c - > P» — ••- •«- Q CA E O d W E > «-• 4- < O C T3 •• O c o — cb TJ a> x « — 0) +_. J> •«- _ £ cooe o C 4^»«- c 4-* c t- a* c « o 01 CA 01 01 O) C N 01 « 4-» sj- i_ •- fy L. D O O -c5iil!Q-,icS t- 4> 01 41 o i a. o cu we- u --- J 5 41 41 O 4-» 4»» Sk — ^ ..- 3 «4- O 3 O jb > 4IV1 T) Q. (A «- E > 4) V ae oeu CA c_ ou co (A 4> 4> 41 — ' ?4I <- CO > i- > 3 -x o o o 01 .- .- 4-> 4) 0 41 O 41 C- Q.U 5 4> .^4) 1- 41 •-' > 41 Ul 41 L. •- C J^ J^ CO g " .2 . o. i a . iu x^ T} CA i-u> d> t» U V 4^ O 41 4)41 4-< X 3 X <— w > <- o .^ 6 •- C •- O c. 41 i. t- co CA UO 4-» 4- 4>4-» X C 4iu tf a -OS u O ae "S E « E X — • §** U 4>* 4> 1-4) CO c co o ^ Of <-• U St. 2 1- U.W O u- U 3 »~ C. U II II II 4* W II H a. < o * + * « z * + CO * « + Appendix E - 11 ------- The comparative method of measuring thermal conductivity has been proposed as an ASTM test method under the name "Guarded, Comparative, Longitudinal Heat Flow Technique". A thermal heat flow circuit is used which is the analog of an electrical circuit with resistances in series. A reference material is chosen to have a thermal conductivity close to that estimated for the sample. Reference standards (also known as heat meters) having the same cross-sectional dimensions as the sample are placed above and below the sample. An upper heater, a lower heater, and a heat sink are added to the "stack" to complete the heat flow circuit. See Figure 1. Appendix F - 1 ------- GUARD GRADIENT STACK GRADIENT" THERMOCOUPLE BOTTOM REFERENCE SAMPLE LOWER; STACK HEAER LIQUID HEAT COOLED SINK HEAT FLOW DIRECTION •v — ' UPPER GUARD HEATER / K A/ \ / K LOWER GUARD HEATER FIGURE 1 SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD Appendix F - 2 ------- The temperature gradients (analogous to potential differences) along the stack are measured with type K (chromel/alumel) thermocouples placed at known separations. The thermocouples are placed into holes or grooves in the references and also in the sample whenever the sample is thick enough to accommodate them. For molten samples, pastes, greases, and other materials that must be contained, the material is placed into a cell consisting of a top and bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2 inch in diameter and .5 inch thick. Thermocouples are not placed into the sample but rather the temperatures measured in the Pyrex are extrapolated to give the temperature at the top and bottom surfaces of the sample material. The Pyrex disks also serve as the thermal conductivity reference material. The stack is clamped with a reproducible load to insure intimate contact between the components. In order to produce a linear flow of heat down the stack and reduce the amount of heat that flows radially, a guard tube is placed around the stack and the intervening space is filled with insulating grains or powder. The temperature gradient in the guard is matched to that in the stack to further reduce radial heat flow. The comparative method is a steady state method of • measuring thermal conductivity. When equilibrium is reached the heat flux (analogous to current flow) down the stack can be determined from the references. The heat into the sample is given by Appendix F - 3 January 1988 ------- - xtop(dT/dx)top and the heat out of the sample is given by where bottom X = thermal conductivity dT/dx = temperature gradient and top refers to the upper reference while bottom refers to the lower reference. If the heat was confined to flow just down the stack, then Q^n and Qout would be equal. If Q^n and Qout are in reasonable agreement, the average heat flow is calculated from - Win + Qout>/2' The sample thermal conductivity is then found from Appendix F - 4 tnnn January 1988 ------- ^sample " Q/(dT/dx)sample The result for the K102 Activated Charcoal Waste tested here is given in Table 1. The sample was held at an average temperature of 42C with a 53C temperature drop across the sample for approximately 20 hours before the temperature profile became steady and the conductivity measured. At the conclusion of the test it appeared that some "drying" of the sample had occurred. Appendix F - 5 -------


            United States        Office of         EPA/530-SW-88-0009-g
EPA/530-SW-88-OOUyg Environmental Protection     SolidWaste        Apnl1988
            Agency          Washington, D.C. 20460
            Solid Waste
 4>EPA      Best                  Proposed
                                     MIVIRONMENTA*
                                      PROTECTION
            Available Technology   AGENCY
                                     ^MUtAs- TEXAC
            (BDAT) Background
            Document for
            Aniline Production
            Treatability Group
            (K103, K104)

            Volume 7

-------
                              FINAL
          BEST DEMONSTRATED AVAILABLE TECHNOLOGY  (BOAT)
              BACKGROUND DOCUMENT FOR K103  AND K104
                            Volume  7
              U. S. Environmental Protection Agency
                      Office of Solid Waste
                        401  M Street,  S.W.
                      Washington,  D.C.  20460
James R. Berlow, Chief
Treatment Technology Section
                            April  1988

-------
            BOAT BACKGROUND DOCUMENT FOR K103  and K104
                        TABLE OF CONTENTS
VOLUME 7                                                     Page

Executive Summary 	      i

BOAT Treatment Standards for K103 and K104	     vii

SECTION 1.  Introduction  	     1-1

SECTION 2.  Industries Affected and Waste
            Characterization  	     2-1

SECTION 3.  Demonstrated/Applicable Treatment
            Technologies  	     3-1

SECTION 4.  Selection of BOAT	     4-1

SECTION 5.  Determination of Regulated Constituents . .  .     5-1

SECTION 6.  Calculation of Treatment Standard   	     6-1

SECTION 7.  Conclusions 	     7-1

APPENDIX A  Statistical Analysis  	     A-l

APPENDIX B  Analysis of Variance Tests  	     B-l

APPENDIX C  Detection Limits for Constituents in the
            Untreated and Treated Waste 	     C-l

APPENDIX D  Calculation of Treatment Standards  	     D-l

APPENDIX E  Analytical QA/QC  	     E-l

APPENDIX F  Thermal Conductivity Summary  	     F-l
                                                           Rev. 3

-------
                        EXECUTIVE SUMMARY








            BOAT Treatment  Standards  for  K103  and  K104








     Pursuant to the Hazardous and Solid Waste Amendments (HSWA)



enacted on November 8, 1984, and in accordance with the



procedures for establishing treatment standards under section



3004 (m) of the Resource Conservation and Recovery Act (RCRA),



the Environmental Protection Agency  (EPA) is proposing treatment



standards for the listed wastes, K103 and K104, based on the



performance of treatment technologies determined by the Agency to



represent Best Demonstrated Available Technology  (BOAT).  This



background document provides the detailed analyses that support



this determination.








     These BDAT treatment standards represent maximum acceptable



concentration levels for selected hazardous constituents in the



wastes or residuals from treatment and/or recycling.  These



levels are established as a prerequisite for disposal of these



wastes in units designated as land disposal units according to 40



CFR 268 (Code of Federal Regulations).   Wastes which, as



generated, contain the regulated constituents at concentrations



which do not exceed the treatment standards are not restricted



from land disposal units.  The Agency has chosen to set levels



for these wastes rather than designating the use of a specific



treatment technology.  The Agency believes that this allows the
                                                           Rev. 3

-------
generators of these wastes a greater degree of flexibility in

selecting a technology or train of technologies that can achieve

these levels.  These standards become effective as of August 8,

1988, as described in the schedule set forth in 40 CFR 268.10.




     According to 40 CFR 261.32 (hazardous wastes from specific

sources) waste codes K103 and K104 are from the

nitrobenzene/aniline industry and are listed as follows:


     K103:     Process residues from aniline extraction from the
               production of aniline.

     K104:     Combined wastewater streams generated from
               nitrobenzene/aniline production.


     Descriptions of the industry and specific processes

generating these wastes, as well as descriptions of the physical

and chemical waste characteristics, are provided in Section 2.0

of this document.  The four digit Standard Industrial

Classification (SIC) code most often reported for the industry

generating this waste code is 2869 (nitrobenzene/aniline).  The

Agency estimates that there are six facilities that may

potentially generate wastes identified as K103-K104.



     The Agency has determined that K103/K104 collectively

represent one general treatability group with two subgroups -
                                        y
wastewaters and nonwastewaters.  For the purpose of the land

disposal restrictions rule, wastewaters are defined as wastes

containing less than 1%  (weight basis) filterable solids and less
                                ii                         Rev. 3

-------
than 1% (weight basis) total organic carbon (TOC).   For K103 and

K104 wastes, this definition was amended to include wastewaters

with a TOC content up to 4% (weight basis).  Wastes not meeting

this definition are classified as nonwastewaters.




     These treatability subgroups represent classes of wastes

that have similar physical and chemical properties within each

subgroup.  EPA believes that each waste within these subgroups

can be treated to the same concentrations when similar

technologies are applied.  The Agency has examined the sources of

these two wastes from the nitrobenzene/aniline industry, the

specific similarities in waste composition, potential applicable

and demonstrated technologies, and attainable treatment

performance in order to support a simplified regulatory approach.

While the Agency has not, at this time, specifically identified

additional wastes which would fall into this treatability group

or two subgroups, this does not preclude the Agency from

extrapolating these standards to other wastes, in the future.




     The K103 and K104 wastes, as generated, have a high water

content and are typically classified as wastewaters.  Residues

from the treatment of these wastewaters (such as spent carbon and

the nitrobenzene solvent stream from the nitrobenzene
                                        *
liquid/liquid extractor) are classified as nonwastewaters.  The

K103/K104 nonwastewaters are generated primarily as a result of

the "derived-from rule" and the "mixture-rule" as outlined in 40
                               iii                         Rev. 3

-------
CFR 261.3 (definition of hazardous waste).



     The Agency has proposed BOAT treatment standards for the two

treatability subgroups of the K103 and K104 wastes - wastewaters

and nonwastewaters.  In general,  these treatment standards have

been proposed for a total of five (5)  organic constituents. In

addition, a treatment standard has been proposed for one (1)

inorganic constituent in K104.  The organic constituents that are

proposed for regulation in K103 and K104 wastes codes are as

follows: benzene, aniline, 2,4-dinitrophenol, nitrobenzene, and

phenol.  Total cyanides were also proposed for regulation in

K104.  Sulfide was not proposed for regulation in K103 because

the Agency requires additional analytical data on sulfide to

determine if it was effectively treated by the treatment system.

A detailed discussion of the selection of constituents to be

regulated is presented in Section 5.0 of this document.



     BOAT treatment standards for wastewater K103 and K104 are

proposed based on performance data from a treatment train which

consisted of liquid/liquid extraction followed by steam stripping

and activated carbon adsorption.   Testing was performed on

representative samples of K103 and K104.  Liquid/liquid

extraction followed by steam stripping and activated carbon
                                        v
adsorption was determined to represent the best demonstrated

available technology (BOAT).  This determination was based on a

statistical comparison of performance data.  The Agency collected




                               iv                         Rev. 3

-------
performance data for a treatment train consisting of

liquid/liquid extraction followed by steam stripping and carbon

adsorption.  A statistical comparison was done with this

performance data from liquid/liquid extraction followed by steam

stripping and from liquid/liquid extraction alone.  Based on this

analysis, the Agency has determined that the data for

liquid/liquid extraction followed by steam stripping and

activated carbon adsorption indicated the highest level of

performance.




     BOAT treatment standards for K103 and K104 nonwastewaters

are proposed based on a transfer of treatment standards developed

for K048/K051 nonwastewaters (dissolved air flotation float and

API separator sludge from the petroleum industry).  These

standards were developed based on the incineration of K048/K051

nonwastewaters.  Treatment data were transferred on a constituent

basis from either the same constituent or from constituents

judged to be similar in physical and chemical properties.  A

detailed discussion of the transfer of the data and methodology

is presented in Section 6.0 of this document.



     The following tables list the specific BDAT treatment

standards for wastes identified as K103 and K104.  The Agency is
                                        *
setting standards based on analyses of total composition for both

wastewater and nonwastewater forms of K103 and K104.  The units

for total composition analysis are in parts per million  (mg/kg)
                                                           Rev. 3

-------
on a weight by weight basis for nonwastewaters.   For wastewaters



the units are expressed on a weight per unit volume basis (mg/1).



Testing procedures are specifically identified in the quality



assurance sections of this document.
                               vi                          Rev. 3

-------
          BOAT TREATMENT STANDARDS FOR K103/K104 WASTES

                           WASTEWATER
Regulated Constituents
Total Composition (mg/1)

K103             K104
Benzene
Aniline
2 , 4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides (CN)
0.147
4.450
0.613
0.073
1.391
NR
0.147
4.450
0.613
0.073
1.391
2.683
NR = Not regulated since it is not presented at treatable levels.
                          NONWASTEWATER
     (Nonwastewater forms of K103/K104 represent spent
     carbon from the activated carbon adsorber.  Treatment
     standards were transferred from K019 for benzene,
     aniline, 2,4-dinitrophenol, nitrobenzene, and phenol
     and from K048/K051 for total cyanides).
Regulated Constituents
Total Composition (mg/kg)

K103             K104
Benzene
Aniline
2 , 4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides (CN)
5.96
5.44
5.44
5.44
5.44 .
NR
5.96
5.44
5.44
5.44
5.44
1.48
NR = Not regulated since it is not present at treatable levels,
                               VII
                                                           Rev. 3

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                         1.   INTRODUCTION







     This section of the background document presents a summary



of the legal authority pursuant to which the BDAT treatment



standards were developed, a summary of EPA's promulgated



methodology for developing BDAT, and finally a discussion of the



petition process that should be followed to request a variance



from the BDAT treatment standards.







1.1            Legal Background



1.1.1          Requirements Under HSWA







     The Hazardous and Solid Waste Amendments of 1984 (HSWA),



enacted on November 8, 1984, and which amended the Resource



Conservation and Recovery Act of 1976 (RCRA), impose substantial



new responsibilities on those who handle hazardous waste.  In



particular, the amendments require the Agency to promulgate



regulations that restrict the land disposal of untreated



hazardous wastes.  In its enactment of HSWA, Congress stated



explicitly that "reliance on land disposal should be minimized or



eliminated, and land disposal, particularly landfill and surface



impoundment, should be the least favored method for managing



hazardous wastes" (RCRA section 1002(b)(7*), 42 U.S.C.



6901(b)(7)).
                               1-1                         Rev. 3

-------
     One part of the amendments specifies dates on which

particular groups of untreated hazardous wastes will be

prohibited from land disposal unless "it has been demonstrated to

the Administrator, to a reasonable degree of certainty, that

there will be no migration of hazardous constituents from the

disposal unit or injection zone for as long as the wastes remain

hazardous" (RCRA section 3004(d)(l), (e) (1) , (g) (5) , 42 U.S.C.

6924
     For the purpose of the restrictions, HSWA defines land

disposal "to include, but not be limited to, any placement of ...

hazardous waste in a landfill, surface impoundment, waste pile,

injection well, land treatment facility, salt dome formation,

salt bed formation, or underground mine or cave" (RCRA section

3004(k), 42 U.S.C. 6924 (k)).  Although HSWA defines land disposal

to include injection wells, such disposal of solvents, dioxins,

and certain other wastes, known as the California List wastes, is

covered on a separate schedule (RCRA section 3004 (f) (2), 42

U.S.C. 6924 (f)(2)).  This schedule reguires that EPA develop

land disposal restrictions for deep well injection by

August 8, 1988.



     The amendments also require the Agency to set "levels or
                                         v
methods of treatment, if any, which substantially diminish the

toxicity of the waste or substantially reduce the likelihood of

migration of hazardous constituents from the waste so that
                               1-2                         Rev. 3

-------
short-term and long-term threats to human health and the


environment are minimized" (RCRA section 3004(m)(l), 42 U.S.C.

6924 (m)(l)).  Wastes that meet treatment standards established

by EPA are not prohibited and may be land disposed.  In setting

treatment standards for listed or characteristic wastes, EPA may

establish different standards for particular wastes within a


single waste code with differing treatability characteristics.

One such characteristic is the physical form of the waste.  This

frequently leads to different standards for wastewaters and

nonwastewaters.




     Alternatively, EPA can establish a treatment standard that

is applicable to more than one waste code when, in EPA's

judgment, all the waste can be treated to the same concentration.


In those instances where a generator can demonstrate that the

standard promulgated for the generator's waste cannot be

achieved, the Agency also can grant a variance from a treatment

standard by revising the treatment standard for that particular

waste through rulemaking procedures.  (A further discussion of

treatment variances is provided in Section 1.3.)




     The land disposal restrictions are effective when

promulgated unless the Administrator grants a national variance
                                         V
and establishes a different date (not to exceed 2 years beyond


the statutory deadline) based on "the earliest date on which


adequate alternative treatment, recovery, or disposal capacity
                               1-3                         Rev. 3

-------
which protects human health and the environment will be



available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).







     If EPA fails to set a treatment standard by the statutory



deadline for any hazardous waste in the First Third or Second



Third of the schedule (see section 1.1.2), the waste may not be



disposed in a landfill or surface impoundment unless the facility



is in compliance with the minimum technological requirements



specified in section 3004(o) of RCRA.  In addition, prior to



disposal, the generator must certify to the Administrator that



the availability of treatment capacity has been investigated and



it has been determined that disposal in a landfill or surface



impoundment is the only practical alternative to treatment



currently available to the generator.  This restriction on the



use of landfills and surface impoundments applies until EPA sets



a treatment standard for the waste or until May 8, 1990,



whichever is sooner.  If the Agency fails to set a treatment



standard for any ranked hazardous waste by May 8, 1990, the waste



is automatically prohibited from land disposal unless the waste



is placed in a land disposal unit that is the subject of a



successful "no migration" demonstration (RCRA section 3004(g), 42



U.S.C. 6924(g)).  "No migration" demonstrations are based on



case-specific petitions that show there will be no migration of



hazardous constituents from the unit for as long as the waste



remains hazardous.
                               1-4                         Rev. 3

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1.1.2          Schedule for Developing Restrictions



     Under Section 3004(g) of RCRA, EPA was required to e»tablish

a schedule for developing treatment standards for all wastes that

the Agency had listed as hazardous by November 8, 1984.

Section 3004(g) required that this schedule consider the

intrinsic hazards and volumes associated with each of these

wastes.  The statute required EPA to set treatment standards

according to the following schedule:


     (a)  Solvents and dioxins standards must be promulgated by
               November 8, 1986;

     (b)  The "California List" must be promulgated by July 8,
          1987;

     (c)  At least one-third of all listed hazardous wastes must
          be promulgated by August 8, 1988 (First Third);

     (d)  At least two-thirds of all listed hazardous wastes must
          be promulgated by June 8, 1989 (Second Third); and

     (e)  All remaining listed hazardous wastes and all hazardous
          wastes identified as of November 8, 1984, by one or
          more of the characteristics defined in 40 CFR Part 261
          must be promulgated by May 8, 1990 (Third Third).


     The statute specifically identified the solvent wastes as

those covered under waste codes F001, F002, F003, F004, and F005;

it identified the dioxin-containing hazardous wastes as those

covered under waste codes F020, F021, F022, and F023.



     Wastes collectively known as the California List wastes,

defined under Section 3004(d) of HSWA, are liquid hazardous

wastes containing metals, free cyanides, PCBs,  corrosives  (i.e.,



                               1-5                         Rev. 3

-------
a pH less than or equal to 2.0), and any liquid or nonliquid

hazardous waste containing halogenated organic compounds (HOCs)

above 0.1 percent by weight.  Rules for the California List were

proposed on December 11, 1986, and final rules for PCBs,

corrosives, and HOC-containing wastes were established

August 12, 1987.  In that rule, EPA elected not to establish

standards for metals.  Therefore, the statutory limits became

effective.




     On May 28, 1986, EPA published a final rule (51 FR 19300)

that delineated the specific waste codes that would be addressed

by the First Third, Second Third, and Third Third.  This schedule

is incorporated into 40 CFR 268.10, .11, and .12.




1.2       Summary of Promulgated BOAT Methodology




     In a November 7, 1986, rulemaking, EPA promulgated a

technology-based approach to establishing treatment standards

under section 3004(m).  Section 3004(m) also specifies that

treatment standards must "minimize" long- and short-term threats

to human health and the environment arising from land disposal of

hazardous wastes.



                                         v-
     Congress indicated in the legislative history accompanying

the HSWA that "[t]he requisite levels of [sic] methods of

treatment established by the Agency should be the best that has
                               1-6                         Rev. 3

-------
been demonstrated to be achievable," noting that the intent is



"to require utilization of available technology" and not a



"process which contemplates technology-forcing standards"  (Vol.



130 Cong. Rec. S9178 (daily ed., July 25, 1984)).  EPA has



interpreted this legislative history as suggesting that Congress



considered the requirement under 3004(m) to be met by application



of the best demonstrated and achievable (i.e., available)



technology prior to land disposal of wastes or treatment



residuals.  Accordingly, EPA's treatment standards are generally



based on the performance of the best demonstrated available



technology (BOAT) identified for treatment of the hazardous



constituents.  This approach involves the identification of



potential treatment systems, the determination of whether they



are demonstrated and available, and the collection of treatment



data from well-designed and well-operated systems.








     The treatment standards, according to the statute, can



represent levels or methods of treatment, if any, that



substantially diminish the toxicity of the waste or substantially



reduce the likelihood of migration of hazardous constituents.



Wherever possible, the Agency prefers to establish BOAT treatment



standards as "levels" of treatment (i.e., performance standards)



rather than adopting an approach that would require the use of



specific treatment "methods."  EPA believes that



concentration-based treatment levels offer the regulated



community greater flexibility to develop and implement compliance
                               1-7                         Rev. 3

-------
strategies as well as an incentive to develop innovative
technologies.

1.2.1     Waste Treatability Group

     In developing the treatment standards, EPA first
characterizes the waste(s).   As necessary, EPA may establish
treatability groups for wastes having similar physical and
chemical properties.  That is, if EPA believes that wastes
represented by different waste codes could be treated to similar
concentrations using identical technologies, the Agency combines
the codes into one treatability group.  EPA generally considers
wastes to be similar when they are both generated from the same
industry and from similar processing stages.  In addition, EPA
may combine two or more separate wastes into the same
treatability group when data are available showing that the waste
characteristics affecting performance are similar or that one
waste would be expected to be less difficult to treat.

     Once the treatability groups have been established, EPA
collects and analyzes data on identified technologies used to
treat the wastes in each treatability group.  The technologies
evaluated must be demonstrated on the waste or a similar waste
and must be available for use.
                               1-8                         Rev. 3

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1.2.2          Demonstrated and Available Treatment Technologies




     Consistent with legislative history, EPA considers

demonstrated technologies to be those that are used to treat the

waste of interest or a similar waste with regard to parameters

that affect treatment selection (see November 7, 1986, 51 FR

40588).  EPA also will consider as treatment those technologies

used to separate or otherwise process chemicals and other

materials.  Some of these technologies clearly are applicable to

waste treatment, since the wastes are similar to raw materials

processed in industrial applications.




     For most of the waste treatability groups for which EPA will

promulgate treatment standards, EPA will identify demonstrated

technologies either through review of literature related to

current waste treatment practices or on the basis of information

provided by specific facilities currently treating the waste or

similar wastes.




     In cases where the Agency does not identify any facilities

treating wastes represented by a particular waste treatability

group, EPA may transfer a finding of demonstrated treatment.  To

do this, EPA will compare the parameters affecting treatment
                                         •r
selection for the waste treatability group of interest to other

wastes for which demonstrated technologies already have been

determined.  The parameters affecting treatment selection and
                               1-9                         Rev. 3

-------
their use for this waste are described in Section 3.2 of this


document.  If the parameters affecting treatment selection are


similar, then the Agency will consider the treatment technology


also to be demonstrated for the waste of interest.  For example,


EPA considers rotary kiln incineration a demonstrated technology


for many waste codes containing hazardous organic constituents,


high total organic content, and high filterable solids content,


regardless of whether any facility is currently treating these


wastes.  The basis for this determination is data found in


literature and data generated by EPA confirming the use of rotary


kiln incineration on wastes having the above characteristics.




     If no commercial treatment or recovery operations are


identified for a waste or wastes with similar physical or


chemical characteristics that  affect treatment selection, the


Agency will be unable to identify any demonstrated treatment


technologies for the waste, and, accordingly, the waste will be


prohibited from land disposal (unless handled in accordance with

the exemption and variance provisions of the rule).  The Agency


is, however, committed to establishing treatment standards as


soon as new or improved treatment processes are demonstrated (and

available).



                                         V
     Operations only available at research facilities, pilot- and


bench- scale operations will not be considered in identifying


demonstrated treatment technologies for a waste because these





                               1-10                        Rev. 3

-------
technologies would not necessarily be "demonstrated."



Nevertheless, EPA may use data generated at research facilities



in assessing the performance of demonstrated technologies.







     As discussed earlier, Congress intended that technologies



used to establish treatment standards under Section 3004(m) be



not only "demonstrated," but also available.  To decide whether



demonstrated technologies may be considered "available," the



Agency determines whether they (1) are commercially available and



(2) substantially diminish the toxicity of the waste or



substantially reduce the likelihood of migration of hazardous



constituents from the waste.







     EPA will only set treatment standards based on a technology



that meets the above criteria.  Thus, the decision to classify a



technology as "unavailable" will have a direct impact on the



treatment standard.  If the best technology is unavailable, the



treatment standard will be based on the next best treatment



technology determined to be available.  To the extent that the



resulting treatment standards are less stringent, greater



concentrations of hazardous constituents in the treatment



residuals could be placed in land disposal units.







     There also may be circumstances in which EPA concludes that



for a given waste none of the demonstrated treatment technologies



are "available" for purposes of establishing the 3004(m)
                               1-11                         Rev. 3

-------
treatment performance standards.  Subsequently,  these wastes will

be prohibited from continued placement in or on the land unless

managed in accordance with applicable exemptions and variance

provisions.  The Agency is, however,  committed to establishing

new treatment standards as soon as new or improved treatment

processes become "available."




     (1)  Proprietary or Patented Processes.  If the demonstrated

treatment technology is a proprietary or patented process that is

not generally available, EPA will not consider the technology in

its determination of the treatment standards.  EPA will consider

proprietary or patented processes available if it determines that

the treatment method can be purchased or licensed from the

proprietor or is commercially available treatment.  The services

of the commercial facility offering this technology often can be

purchased even if the technology itself cannot be purchased.




     (2)  Substantial Treatment.  To be considered "available," a

demonstrated treatment technology must "substantially diminish

the toxicity" of the waste or "substantially reduce the

likelihood of migration of hazardous constituents" from the waste

in accordance with section 3004(m).  By requiring that

substantial treatment be achieved in order to set a treatment
                                         V
standard, the statute ensures that all wastes are adequately

treated before being placed in or on the land and ensures that

the Agency does not require a treatment method that provides
                               1-12                         Rev. 3

-------
little or no environmental benefit.  Treatment will always be

deemed substantial if it results in nondetectable levels of the

hazardous constituents of concern.  If nondetectable levels are

not achieved, then a determination of substantial treatment will

be made on a case-by-case basis.  This approach is necessary

because of the difficulty of establishing a meaningful guideline

that can be applied broadly to the many wastes and technologies

to be considered.  EPA will consider the following factors in an

effort to evaluate whether a technology provides substantial

treatment on a case-by-case basis:


     (a)  Number and types of constituents treated;

     (b)  Performance (concentration of the constituents in the
          treatment residuals); and

     (c)  Percent of constituents removed.




     If none of the demonstrated treatment technologies achieve

substantial treatment of a waste, the Agency cannot establish

treatment standards for the constituents of concern in that

waste.




1.2.3          Collection of Performance Data




     Performance data on the demonstrated available technologies
                                         *•
are evaluated by the Agency to determine whether the data are

representative of well-designed and well-operated treatment

systems.  Only data from well-designed and well-operated systems





                               1-13                         Rev. 3

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are included in determining BOAT.  The data evaluation includes

data already collected directly by EPA and/or data provided by

industry.  In those instances where additional data are needed to

supplement existing information, EPA collects additional data

through a sampling and analysis program.  The principal elements

of this data collection program are:  (a) identification of

facilities for site visits, (b) engineering site visit,

(c) Sampling and Analysis Plan,  (d) sampling visit, and (e)

Onsite Engineering Report.




     (1)  Identification of Facilities for Site Visits.  To

identify facilities that generate and/or treat the waste of

concern, EPA uses a number of information sources.  These include

Stanford Research Institute's Directory of Chemical Producers,

EPA's Hazardous Waste Data Management System (HWDMS), the 1986

Treatment, Storage, Disposal Facility (TSDF) National Screening

Survey, and EPA's Industry Studies Data Base.  In addition, EPA

contacts trade associations to inform them that the Agency is

considering visits to facilities in their industry and to solicit

assistance in identifying facilities for EPA to consider in its

treatment sampling program.




     After identifying facilities that treat the waste, EPA uses
                                         v
this hierarchy to select sites for engineering visits:

(1) generators treating single wastes on site; (2) generators

treating multiple wastes together on site;  (3) commercial
                               1-14                         Rev. 3

-------
treatment, storage, and disposal facilities (TSDFs); and (4) EPA



in-house treatment.  This hierarchy is based on two concepts:



(1) to the extent possible, EPA should develop treatment



standards from data produced by treatment facilities handling



only a single waste, and (2) facilities that routinely treat a



specific waste have had the best opportunity to optimize design



parameters.  Although excellent treatment can occur at many



facilities that are not high in this hierarchy, EPA has adopted



this approach to avoid, when possible, ambiguities related to the



mixing of wastes before and during treatment.







     When possible, the Agency will evaluate treatment



technologies using commercially operated systems.  If performance



data from properly designed and operated commercial treatment



methods for a particular waste or a waste judged to be similar



are not available, EPA may use data from research facilities



operations.  Whenever research facility data are used, EPA will



explain why such data were used in the preamble and background



document and will request comments on the use of such data.







     Although EPA's data bases provide information on treatment



for individual wastes, the data bases rarely provide data that



support the selection of one facility for sampling over another.



In cases where several treatment sites appear to fall into the



same level of the hierarchy, EPA selects sites for visits



strictly on the basis of which facility could most expeditiously










                               1-15                         Rev. 3

-------
be visited and later sampled if justified by the engineering



visit.








      (2)  Engineering Site Visit.  Once a treatment facility has



been selected, an engineering site visit is made to confirm that



a candidate for sampling meets EPA's criteria for a well-designed



facility and to ensure that the necessary sampling points can be



accessed to determine operating parameters and treatment



effectiveness.  During the visit, EPA also confirms that the



facility appears to be well operated, although the actual



operation of the treatment system during sampling is the basis



for EPA's decisions regarding proper operation of the treatment



unit.  In general, the Agency considers a well-designed facility



to be one that contains the unit operations necessary to treat



the various hazardous constituents of the waste as well as to



control other nonhazardous materials in the waste that may affect



treatment performance.







     In addition to ensuring that a system is reasonably well



designed, the engineering visit examines whether the facility has



a way to measure the operating parameters that affect performance



of the treatment system during the waste treatment period.  For



example, EPA may choose not to sample a treatment system that



operates in a continuous mode, for which an important operating



parameter cannot be continuously recorded.  In such systems,



instrumentation is important in determining whether the treatment
                               1-16                         Rev. 3

-------
system is operating at design values during the waste treatment



period.







     (3)  Sampling and Analysis Plan.  If after the engineering



site visit the Agency decides to sample a particular plant, the



Agency will then develop a site-specific Sampling and Analysis



Plan (SAP) according to the Generic Quality Assurance Project



Plan for the Land Disposal Restriction Program ("BOAT"),



EPA/530-SW-87-011.  In brief, the SAP discusses where the Agency



plans to sample, how the samples will be taken, the frequency of



sampling, the constituents to be analyzed and the method of



analysis, operational parameters to be obtained,  and specific



laboratory quality control checks on the analytical results.







     The Agency will generally produce a draft of the



site-specific Sampling and Analysis Plan within 2 to 3 weeks of



the engineering visit.  The draft of the SAP is then sent to the



plant for review and comment.  With few exceptions, the draft SAP



should be a confirmation of data collection activities discussed



with the plant personnel during the engineering site visit.  EPA



encourages plant personnel to recommend any modifications to the



SAP that they believe will improve the quality of the data.







     It is important to note that sampling of a plant by EPA does



not mean that the data will be used in the development of



treatment standards for BOAT.  EPA's final decision on whether to
                               1-17                         Rev. 3

-------
use data from a sampled plant depends on the actual analysis of

the waste being treated and on the operating conditions at the

time of sampling.  Although EPA would not plan to sample a

facility that was not ostensibly well-designed and well-operated,

there is no way to ensure that at the time of the sampling the

facility will not experience operating problems.  Additionally,

EPA statistically compares its test data to suitable

industry-provided data, where available, in its determination of

what data to use in developing treatment standards.  The

methodology for comparing data is presented later in this

section.




     (Note: Facilities wishing to submit data for consideration

in the development of BOAT standards should, to the extent

possible, provide sampling information similar to that acquired

by EPA.  Such facilities should review the Generic Quality

Assurance Project Plan for the Land Disposal Restriction Program

("BOAT"), which delineates all of the quality control and quality

assurance measures associated with sampling and analysis.

Quality assurance and quality control procedures are summarized

in Section 1.2.6 of this document.)




     (4)  Sampling Visit.  The purpose of the sampling visit is
                                        v
to collect samples that characterize the performance of the

treatment system and to document the operating conditions that

existed during the waste treatment period.  At a minimum, the
                               1-18                         Rev. 3

-------
Agency attempts to collect sufficient samples of the untreated

waste and solid and liquid treatment residuals so that

variability in the treatment process can be accounted for in the

development of the treatment standards.  To the extent

practicable, and within safety constraints, EPA or its

contractors collect all samples and ensure that chain-of-custody

procedures are conducted so that the integrity of the data is

maintained.




     In general, the samples collected during the sampling visit

will have already been specified in the SAP.  In some instances,

however, EPA will not be able to collect all planned samples

because of changes in the facility operation or plant upsets; EPA

will explain any such deviations from the SAP in its follow-up

Onsite Engineering Report.




     (5)  Onsite Engineering Report.  EPA summarizes all its data

collection activities and associated analytical results for

testing at a facility in a report referred to as the Onsite

Engineering Report (OER).   This report characterizes the waste(s)

treated, the treated residual concentrations, the design and

operating data, and all analytical results including methods used

and accuracy results.  This report also describes any deviations
                                         *•
from EPA's suggested analytical methods for hazardous wastes

(Test Methods for Evaluating Solid Waste, SW-846, Third Edition,

November 1986).
                               1-19                         Rev. 3

-------
     After the Onsite Engineering Report is completed, the report



is submitted to the plant for review.  This review provides the



plant with a final opportunity to claim any information contained



in the report as confidential.  Following the review and



incorporation of comments, as appropriate, the report is made



available to the public with the exception of any material



claimed as confidential by the plant.







1.2.4     Hazardous Constituents Considered and Selected for



          Regulation








     (1)  Development of BOAT List.  The list of hazardous



constituents within the waste codes that are targeted for



treatment is referred to by the Agency as the BDAT constituent



list.  This list, provided as Table 1-1, is derived from the



constituents presented in 40 CFR Part 261, Appendix VII and



Appendix VIII, as well as several ignitable constituents used as



the basis of listing wastes as F003 and F005.  These sources



provide a comprehensive list of hazardous constituents



specifically regulated under RCRA.  The BDAT list consists of



those constituents that can be analyzed using methods published



in SW-846, Third Edition.








     The initial BDAT constituent list was published in EPA's



Generic Quality Assurance Project Plan, March 1987



(EPA/530-SW-87-011).  Additional constituents will be added to
                               1-20                        Rev. 3

-------
1521g
                  Table 1-1  BOAT Constituent List
BOAT
reference
no.

222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32
Parameter
Volatiles
Acetone
Acetomtn le
Acrolein
Acrylomtnle
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 , 2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromomethane
Trans -1 ,4-Dichloro-2-butene
Dichlorodif luorome thane
1, 1-Oichloroethane
1,2-Oichloroethane
1,1-Dichloroethylene
Trans-1 , 2-Dichloroethene
1,2-Oichloropropane
Trans-1 ,3-Oichloropropene
cis-1 ,3-Dichloropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyan'de
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Cas no.

67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
60-29-7
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
                                  1-21                                   Rev.  3

-------
1521g
                      Table 1-1  (continued)
BOAT
reference
no.

33.
228.
34.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.

50.
215.
216.
217.

51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
Parameter
Volatiles (continued)
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1,1, 1,2-Tetrachloroethane
1,1,2, 2-Tet rach loroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Tnchloroethene
Tr i ch loromonof luoromethane
1,2,3-Trichloropropane
l,l,2-Trichloro-l,2,2-tnf luoro-
ethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Sennvolat i les
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Cas no.

78-83-1
67-56-1
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1

75-01-4
97-47-6
108-38-3
106-44-5

208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5

50-32-8
                                 1-22                                  Rev.  3

-------
1521g
                      Table 1-1  (continued)
BOAT
reference
no.

63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.'
87.
88.
89.
90.
91.
92.
93.
94.
95
96.
97.
98.
99
100.
101.
Parameter
Semivolatiles (continued)
Benzo(b)f luoranthene
Benzo(ghi )pery lene
Benzo(k)f luoranthene
p-Benzoquinone
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani line
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
0 i benz( a, h) anthracene
Dibenzo(a,e)pyrene
Oibenzo(a, i)pyrene
m-Oichlorobenzene
o-Dichlorobenzene
p-Oichlorobenzene
3,3'-Oichlorobenzidine
2,4-Oichlorophenol
2,6-Oichlorophenol
Diethyl phthalate
3,3'-Dimethoxybenzidine
p-D imethy lami noazobenzene
3,3'-Oimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Oinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
CAS no.

205-99-2
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-ll-*3
84-74-2
100-25-4
534-52-1
51-28-5
                                 1-23                                  Rev.  3

-------
ISZlg
                      Table 1-1  (continued)
BOAT
reference
no.

102.
103.
104.
105.
106.
219.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.

36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
Parameter
Semivolatlles (continued)
2,4-Dinitrotoluene
2,6-Oinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosannne
Diphenylamine
D 1 pheny 1 n i t rosam i ne
1 , 2-D ipheny Ihydraz i ne
Fluoranthene
Fluorene
Hexach lorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
Indeno(l,2,3-cd)pyrene
Isosafrole
Methapyri lene
3-Met hy 1cho lanthrene
4,4'-Methylenebis
(2-chloroamline)
Methyl methanesulfonate
Naphthalene
1 ,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosomethylethylamine
N-Nitrosomorpholine
N-Nitrosopipendine
n-Nitrosopyrrolidine
5-Nitro-o-toluidine
Pentachlorobenzene
Pentach loroethane
Pentach loron i t robenzene
CAS no.

121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1 -
91-80-5
56-49-5

101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-7
99-65-8
608-93-5
76-01-7
82-68-8
                                  1-24                                  Rev.  3

-------
1521g
                      Table 1-1  (continued)
BOAT
reference
no.

139.
140.
141.
142.
220.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.


154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
168.

169.
170.
171.
Parameter
Semivolatiles (continued)
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1 , 2 , 4 , 5-Tetrach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1 . 2 , 4-Tr i en lorobenzene
2, 4, 5-Tnch loropheno 1
2, 4, 6-Tricn loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Metals
Antimony
Arsenic
Barium
Beryl lium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Tha 1 1 i urn
Vanadium
Zinc
Inorganics
Cyanide
Fluoride
Sulfide
CAS no.

87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2

126-72-7

7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-6&-6

57-12-5
16964-48-8
8496-25-8
                                1-25
Rev.  3

-------
1521g
                      Table 1-1  (continued)
BOAT
reference
no.

172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.

192.
193.
194.

195.
196.
197.
198.
199.

200.
201.
202.
Parameter
Orqanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
ganma-BHC
Chlordane
ODD
DOE
DDT
Dieldrin
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
tCepone
Methoxyclor
Toxaphene
Phenoxvacet ic acid herbicides
2,4-Dichlorophenoxyacetic acid
Si Ivex
2.4,5-T
Orqanoohosphorous insecticides
Disulfoton
Fampnur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.

309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2

94-75-7
93-72-1
93-76-5

298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
V
12674-11-2
11104-28-2
11141-16-5
                                 1-26
Rev.  3

-------
1521g
                          Table 1-1  (continued)
BOAT
reference          Parameter                             CAS no.
               PCBs  (continued)

203.            Aroclor  1242                             53469-21-9
204.            Aroclor  1248                             12672-29-6
205.            Aroclor  1254                             11097-69-1
206.            Aroclor  1260                             11096-82-5

               Oioxins  and furans

207.            Hexachlorodibenzo-p-dioxins
208.            Hexachlorodibenzofurans
209.            Pentachlorodibenzo-p-dioxins
210.            Pentachlorodibenzofurans
211.            Tetrachlorodibenzo-p-dioxins
212.            Tetrachlorodibenzofurans
213.            2,3,7,8-Tetrachlorodibenzo-p-dioxin      1746-01-6
                                       1-27                                         Rev.  3

-------
the BOAT constituent list as additional key constituents are



identified for specific waste codes or as new analytical methods



are developed for hazardous constituents.  For example, since the



list was published in March 1987, eighteen additional



constituents (hexavalent chromium, xylene (all three isomers),



benzal chloride, phthalic anhydride, ethylene oxide, acetone,



n-butyl alcohol, 2-ethoxyethanol, ethyl acetate, ethyl benzene,



ethyl ether, methanol, methyl isobutyl ketone, 2-nitropropane,



l,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have



been added to the list.







     Chemicals are listed in Appendix VIII if they are shown in



scientific studies to have toxic, carcinogenic, mutagenic, or



teratogenic effects on humans or other life-forms, and they



include such substances as those identified by the Agency's



Carcinogen Assessment Group as being carcinogenic.  Including a



constituent in Appendix VIII means that the constituent can be



cited as a basis for listing toxic wastes.







     Although Appendix VII, Appendix VIII, and the F003 and F005



ignitables provide a comprehensive list of RCRA-regulated



hazardous constituents, not all of the constituents can be



analyzed in a complex waste matrix.  Therefore, constituents that



could not be readily analyzed in an unknown waste matrix were not



included on the initial BOAT list.  As mentioned above, however,



the BDAT constituent list is a continuously growing list that










                               1-28                        Rev. 3

-------
does not preclude the addition of new constituents when

analytical methods are developed.



     There are 5 major reasons that constituents were not

included on the BOAT constituent list:
     (a)   Constituents are unstable.  Based on their chemical
          structure, some constituents will either decompose in
          water or will ionize.  For example, maleic anhydride
          will form maleic acid when it comes in contact with
          water and copper cyanide will ionize to form copper and
          cyanide ions.  However, EPA may choose to regulate the
          decomposition or ionization products.
     (b)  EPA-approved or verified analytical methods are not
          available.  Many constituents, such as
          1,3,5-trinitrobenzene, are not measured adequately or
          even detected using any of EPA's analytical methods
          published in SW-846 Third Edition.
     (c)  The constituent is a member of a chemical group
          designated in Appendix VIII as not otherwise specified
          (N.O.S.).  Constituents listed as N.O.S., such as
          chlorinated phenols, are a generic group of some types
          of chemicals for which a single analytical procedure is
          not available.  The individual members of each such
          group need to be listed to determine whether the
          constituents can be analyzed.  For each N.O.S. group,
          all those constituents that can be readily analyzed are
          included in the BDAT constituents list.
     (d)  Available analytical procedures are not appropriate for
          a complex waste matrix.  Some compounds, such as
          auramine, can be analyzed as a pure constituent.
          However, in the presence of other constituents, the
          recommended analytical method does not positively
          identify the constituent.  The use of high pressure
          liquid chromotography (HPLC) presupposes a high
          expectation of finding the specific constituents of
          interest.  In using this procedure to screen samples,
          protocols would have to be developed on a case-specific
          basis to verify the identity of constituents present in
          the samples.  Therefore, HPLC is not an appropriate
          analytical procedure for complex samples containing
                               1-29                         Rev. 3

-------
          unkown constituents.
     (e)   Standards for analytical instrument calibration are not
          commercially available.   For several constituents, such
          as benz(c)acridine,  commercially available standards of
          a "reasonably" pure grade are not available.  The
          unavailability of a standard was determined by a review
          of catalogs from specialty chemical manufacturers.
     Two constituents (fluoride and sulfide)  are not specifically

included in Appendices VII and VIII; however, these compounds are

included on the BOAT list as indicator constituents for compounds

from Appendices VII and VIII such as hydrogen fluoride and

hydrogen sulfide, which ionize in water.



     The BOAT constituent list presented in Table 1-1 is divided

into the following nine groups:

          o    Volatile organics
          o    Semivolatile organics
          o    Metals
          o    Other inorganics
          o    Organochlorine pesticides
          o    Phenoxyacetic acid herbicides
          o    Organophosphorous insecticides
          o    PCBs
          o    Dioxins and furans

The constituents were placed in these categories based on their

chemical properties.  The constituents in each group are expected

to behave similarily during treatment and are also analyzed, with

the exception of the metals and inorganics, by using the same
                                         y
analytical methods.
                               1-30                         Rev. 3

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     (2)  Constituent Selection Analysis.  The constituents that



the Agency selects for regulation in each treatability group are,



in general, those found in the untreated wastes at treatable



concentrations.  For certain waste codes, the target list for the



untreated waste may have been shortened  (relative to analyses



performed to test treatment technologies) because of the extreme



unlikelihood of the constituent being present.







     In selecting constituents for regulation, the first step is



to summarize all the constituents that were found in the



untreated waste at treatable concentrations.  This process



involves the use of the statistical analysis of variance (ANOVA)



test, described in Section 1.2.6, to determine if constituent



reductions were significant.  The Agency interprets a significant



reduction in concentration as evidence that the technology



actually "treats" the waste.







     There are some instances where EPA may regulate constituents



that are not found in the untreated waste but are detected in the



treated residual.  This is generally the case where presence of



the constituents in the untreated waste interferes with the



quantification of the constituent of concern.  In such instances,



the detection levels of the constituent are relatively high,



resulting in a finding of "not detected" when, in fact, the



constituent is present in the waste.
                              1-31                         Rev. 3

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     After determining which of the constituents in the untreated

waste are present at treatable concentrations, EPA develops a

list of potential constituents for regulation.  The Agency then

reviews this list to determine if any of these constituents can

be excluded from regulation because they would be controlled by

regulation of other constituents in the list.




     EPA performs this indicator analysis for two reasons: (1) it

reduces the analytical cost burdens on the treater and (2) it

facilitates implementation of the compliance and enforcement

program.  EPA's rationale for selection of regulated constituents

for this waste code is presented in Section 5 of this background

document.




     (3)  Calculation of Standards.  The final step in the

calculation of the BDAT treatment standard is the multiplication

of the average treatment value by a factor referred to by the

Agency as the variability factor.  This calculation takes into

account that even well-designed and well-operated treatment

systems will experience some fluctuations in performance.  EPA

expects that fluctuations will result from inherent mechanical

limitations in treatment control systems, collection of treated

samples, and analysis of these samples.  All of the above
                                         V
fluctuations can be expected to occur at well-designed and

well-operated treatment facilities.  Therefore, setting treatment

standards utilizing a variability factor should be viewed not as





                               1-32                         Rev. 3

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a relaxing of 3004(m) requirements, but rather as a function of
the normal variability of the treatment processes.  A treatment
facility will have to be designed to meet the mean achievable
treatment performance level to ensure that the performance levels
remain within the limits of the treatment standard.

     The Agency calculates a variability factor for each
constituent of concern within a waste treatability group using
the statistical calculation presented in Appendix A.  The
equation for calculating the variability factor is the same as
that used by EPA for the development of numerous regulations in
the Effluent Guidelines Program under the Clean Water Act.  The
variability factor establishes the instantaneous maximum based on
the 99th percentile value.

     There is an additional step in the calculation of the
treatment standards in those instances where the ANOVA analysis
shows that more than one technology achieves a level of
performance that represents BOAT.  In such instances, the BOAT
treatment standard is calculated by first averaging the mean
performance value for each technology for each constituent of
concern and then multiplying that value by the highest
variability factor among the technologies considered.  This
procedure ensures that all the BOAT technologies used as the
basis for the standards will achieve full compliance.
                               1-33                         Rev. 3

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1.2.5          Compliance with Performance Standards




     All the treatment standards reflect performance achieved by

the Best Demonstrated Available Technology (BOAT).   As such,


compliance with these standards only requires that the treatment

level be achieved prior to land disposal.  It does not require

the use of any particular treatment technology.  While dilution

of the waste as a means to comply with the standard is

prohibited, wastes that are generated in such a way as to

naturally meet the standard can be land disposed without

treatment.  With the exception of treatment standards that

prohibit land disposal, all treatment standards proposed are

expressed as a concentration level.




     EPA has used both total constituent concentration and TCLP

analyses of the treated waste as a measure of technology


performance.  EPA's rationale for when each of these analytical

tests is used is explained in the following discussion.




     For all organic constituents, EPA is basing the treatment

standards on the total constituent concentration found in the

treated waste.  EPA based its decision on the fact that


technologies exist to destroy the various organics compounds.
                                         V
Accordingly, the best measure of performance would be the extent

to which the various organic compounds have been destroyed or the

total amount of constituent remaining after treatment.  (NOTE:





                               1-34                        Rev. 3

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EPA's land disposal restrictions for solvent waste codes

F001-F005 (51 FR 40572) uses the TCLP value as a measure of

performance.  At the time that EPA promulgated the treatment

standards for F001-F005, useful data were not available on total

constituent concentrations in treated residuals and, as a result,

the TCLP data were considered to be the best measure of

performance.)




     For all metal constituents, EPA is using both total

constituent concentration and/or the TCLP as the basis for

treatment standards.  The total constituent concentration is

being used when the technology basis includes a metal recovery

operation.  The underlying principle of metal recovery is the

reduction of the amount of metal in a waste by separating the

metal for recovery; therefore, total constituent concentration in

the treated residual is an important measure of performance for

this technology.  Additionally, EPA also believes that it is

important that any remaining metal in a treated residual waste

not be in a state that is easily leachable; accordingly, EPA is

also using the TCLP as a measure of performance.  It is important

to note that for wastes for which treatment standards are based

on a metal recovery process, the facility has to comply with both

the total constituent concentration and the TCLP prior to land
                                         *•
disposal.
                               1-35                         Rev. 3

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     In cases where treatment standards for metals are not based

on recovery techniques but rather on stabilization, EPA is using

only the TCLP as a measure of performance.   The Agency's

rationale is that stabilization is not meant to reduce the

concentration of metal in a waste but only to chemically minimize

the ability of the metal to leach.



1.2.6          Identification of BOAT



     (1)  Screening of Treatment Data.  This section explains how

the Agency determines which of the treatment technologies

represent treatment by BOAT.  The first activity is to screen the

treatment performance data from each of the demonstrated and

available technologies according to the following criteria:


     (a)  Design and operating data associated with the treatment
          data must reflect a well-designed, well-operated system
          for each treatment data point.  (The specific design
          and operating parameters for each demonstrated
          technology for this waste code are discussed in Section
          3.2 of this document.)


     (b)  Sufficient QA/QC data must be available to determine
          the true values of the data from the treated waste.
          This screening criterion involves adjustment of treated
          data to take into account that the type value may be
          different from the measured value.  This discrepancy
          generally is caused by other constituents in the waste
          that can mask results or otherwise interfere with the
          analysis of the constituent of concern.


     (c)  The measure of performance must be consistent with
          EPA's approach to evaluating treatment by type of
          constituents (e.g., total concentration data for
          organics, and total concentration and TCLP for metals
          in the leachate from the residual).



                               1-36                         Rev. 3

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     In the absence of data needed to perform the screening



analysis, EPA will make decisions on a case-by-case basis of



whether to include the data.  The factors included in this



case-by-case analysis will be the actual treatment levels



achieved, the availability of the treatment data and their



completeness (with respect to the above criteria),  and EPA's



assessment of whether the untreated waste represents the waste



code of concern.  EPA's application of these screening criteria



for this waste code are provided in Section 4 of this background



document.







     (2)  Comparison of Treatment Data.  In cases in which EPA



has treatment data from more than one technology following the



screening activity, EPA uses the statistical method known as



analysis of variance (ANOVA) to determine if one technology



performs significantly better.  This statistical method



(summarized in Appendix A) provides a measure of the differences



between two data sets.   If EPA finds that one technology performs



significantly better (i.e., the data sets are not homogeneous),



BOAT treatment standards are the level of performance achieved by



the best technology multiplied by the corresponding variability



factor for each regulated constituent.







     If the differences in the data sets are not statistically



significant, the data sets are said to be homogeneous.



Specifically, EPA uses the analysis of variance to determine







                               1-37                         Rev. 3

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whether BOAT represents a level of performance achieved by only

one technology or represents a level of performance achieved by

more than one (or all) of the technologies.  If the Agency finds

that the levels of performance for one or more technologies are

not statistically different, EPA averages the performance values

achieved by each technology and then multiplies this value by the

largest variability factor associated with any of the

acceptable technologies.  A detailed discussion of the treatment

selection method and an example of how EPA chooses BOAT from

multiple treatment systems is provided in Appendix A.




     (3)  Quality Assurance/Quality Control.  This section

presents the principal quality assurance/quality control  (QA/QC)

procedures employed in screening and adjusting the data to be

used in the calculation of treatment standards.  Additional QA/QC

procedures used in collecting and screening data for the BOAT

program are presented in EPA's Generic Quality Assurance Project

Plan for Land Disposal Restrictions Program ("BOAT")

(EPA/530-SW-87-001, March 1987).




     To calculate the treatment standards for the Land Disposal

Restriction Rules, it is first necessary to determine the

recovery value for each constituent (the amount of constituent
                                         V
recovered after spiking, which is the addition of a known amount

of the constituent, minus the initial concentration in the

samples divided by the amount added) for a spike of the treated
                               1-38                        Rev. 3

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residual.  Once the recovery value is determined, the following

procedures are used to select the appropriate percent recovery

value to adjust the analytical data:


     (a)  If duplicate spike recovery values are available for
          the constituent of interest, the data are adjusted by
          the lowest available percent recovery value (i.e., the
          value that will yield the most conservative estimate of
          treatment achieved).  However, if a spike recovery
          value of less than 20 percent is reported for a
          specific constituent, the data are not used to set
          treatment standards because the Agency does not have
          sufficient confidence in the reported value to set a
          national standard.
     (b)  If data are not available for a specific constituent
          but are available for an isomer, then the spike
          recovery data are transferred from the isomer and the
          data are adjusted using the percent recovery selected
          according to the procedure described in (a) above.


     (c)  If data are not available for a specific constituent
          but are available for a similar class of constituents
          (e.g., volatile organics, acid-extractable
          semivolatiles), then spike recovery data available for
          this class of constituents are transferred.  All spike
          recovery values greater than or equal to 20 percent for
          a spiked sample are averaged and the constituent
          concentration is adjusted by the average recovery
          value.  If spiked recovery data are available for more
          than one sample, the average is calculated for each
          sample and the data are adjusted by the lowest average
          value.
     (d)  If matrix spike recovery data are not available for a
          set of data to be used to calculate treatment
          standards, then matrix spike recovery data are
          transferred from a waste that the Agency believes is a
          similar matrix (e.g., if the data are for an ash from
          incineration, then data from other incinerator ashes
          could be used).  While EPA recognizes that transfer of
          matrix spike recovery data from a similar waste is not
          an exact analysis, this is considered the best approach
          for adjusting the data to account for the fact that
          most analyses do not result in extraction of 100
          percent of the constituent.  In assessing the recovery
                              1-39                         Rev. 3

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          data to be transferred, the procedures outlined in (a),
          (b), and (c)  above are followed.
     The analytical procedures employed to generate the data used
to calculate the treatment standards are listed in Appendix E of
this document.  In cases where alternatives or equivalent
procedures and/or equipment are allowed in EPA's SW-846, Third
Edition (November 1986) methods, the specific procedures and
equipment used are also documented in this Appendix.  In
addition, any deviations from the SW-846, Third Edition, methods
used to analyze the specific waste matrices are documented.  It
is important to note that the Agency will use the methods and
procedures delineated in Appendix E to enforce the treatment
standards presented in Section 6 of this document.  Accordingly,
facilities should use these procedures in assessing the
performance of their treatment systems.

1.2.7     BOAT Treatment Standards for "Derived-From" and "Mixed"
          Wastes

     (1)  Wastes from Treatment Trains Generating Multiple
Residues.  In a number of instances, the proposed BOAT consists
of a series of operations each of which generates a waste
residue.  For example, the proposed BDATvfor a certain waste code
is based on solvent extraction, steam stripping, and activated
carbon adsorption.  Each of these treatment steps generates a
waste requiring treatment — a solvent-containing stream from

                               1-40                        Rev. 3

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solvent extraction, a stripper overhead, and spent activated

carbon.  Treatment of these wastes may generate further residues;

for instance, spent activated carbon (if not regenerated) could

be incinerated, generating an ash and possibly a scrubber water

waste.  Ultimately, additional wastes are generated that may

require land disposal.  With respect to these wastes, the Agency

wishes to emphasize the following points:
     (a)  All of the residues from treating the original listed
          wastes are likewise considered to be the listed waste
          by virtue of the derived-from rule contained in 40 CFR
          Part 261.3(c)(2).  (This point is discussed more fully
          in (2) below.)  Consequently, all of the wastes
          generated in the course of treatment would be
          prohibited from land disposal unless they satisfy the
          treatment standard or meet one of the exceptions to the
          prohibition.
     (b)  The Agency's proposed treatment standards generally
          contain a concentration level for wastewaters and a
          concentration level for nonwastewaters.   The treatment
          standards apply to all of the wastes generated in
          treating the original prohibited waste.   Thus, all
          solids generated from treating these wastes would have
          to meet the treatment standard for nonwastewaters.  All
          derived-from wastes meeting the Agency definition of
          wastewater (less than 1 percent TOC and less than 1
          percent total filterable solids) would have to meet the
          treatment standard for wastewaters.  EPA wishes to make
          clear that this approach is not meant to allow partial
          treatment in order to comply with the applicable
          standard.
     (c)  The Agency has not performed tests, in all cases, on
          every waste that can result from every part of the
          treatment train.  However, the Agency's treatment
          standards are based on treatment of the most
          concentrated form of the waste.  Consequently, the
          Agency believes that the less concentrated wastes
          generated in the course of treatment will also be able
          to be treated to meet this value.
                              1-41                         Rev. 3

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     (2)   Mixtures and Other Derived-From Residues.  There is a

further question as to the applicability of the BOAT treatment

standards to residues generated not from treating the waste (as

discussed above),  but from other types of management.  Examples

are contaminated soil or leachate that is derived from managing

the waste.  In these cases, the mixture is still deemed to be the

listed waste, either because of the derived-from rule (40 CFR

Part 261.3(c)(2)(i)) or the mixture rule (40 CFR Part

261.3(a)(2)(iii) and (iv) or because the listed waste is

contained in the matrix  (see, for example, 40 CFR Part

261.33(d)).  The prohibition for the particular listed waste

consequently applies to this type of waste.




     The Agency believes that the majority of these types of

residues can meet the treatment standards for the underlying

listed wastes (with the possible exception of contaminated soil

and debris for which the Agency is currently investigating

whether it is appropriate to establish a separate treatability

subcategorization).  For the most part, these residues will be

less concentrated than the original listed waste.  The Agency's

treatment standards also make a generous allowance for process

variability by assuming that all treatability values used to

establish the standard are lognormally distributed.  The waste
                                         y
also might be amenable to a relatively nonvariable form of

treatment technology such as incineration.  Finally, and perhaps

most important, the rules contain a treatability variance that





                               1-42                         Rev. 3

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allows a petitioner to demonstrate that its waste cannot be



treated to the level specified in the rule (40 CFR Part



268.44(a).  This provision provides a safety valve that allows



persons with unusual waste matrices to demonstrate the



appropriateness of a different standard.  The Agency, to date,



has not received any petitions under this provision  (for example,



for residues contaminated with a prohibited solvent waste),



indicating, in the Agency's view, that the existing standards are



generally achievable.







     (3)  Residues from Managing Listed Wastes or that Contain



Listed Wastes.  The Agency has been asked if and when residues



from managing hazardous wastes, such as leachate and contaminated



ground water, become subject to the land disposal prohibitions.



Although the Agency believes this question to be settled by



existing rules and interpretative statements, to avoid any



possible confusion the Agency will address the question again.








     Residues from managing First Third wastes, listed California



List wastes, and spent solvent and dioxin wastes are all



considered to be subject to the prohibitions for the underlying



hazardous waste.  Residues from managing California List wastes



likewise are subject to the California List prohibitions when the



residues themselves exhibit a characteristic of hazardous waste.



This determination stems directly from the derived-from rule in



40 CFR Part 261.3(c)(2) or in some cases from the fact that the
                               1-43                         Rev. 3

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waste is mixed with or otherwise contains the listed waste.  The
underlying principle stated in all of these provisions is that
listed wastes remain listed until delisted.

     The Agency's historic practice in processing delisting
petitions addressing mixing residuals has been to consider them
to be the listed waste and to require that delisting petitioners
address all constituents for which the derived-from waste  (or
other mixed waste) was listed.  The language in 40 CFR Part
260.22(b) states that mixtures or derived-from residues can be
delisted provided a delisting petitioner makes a demonstration
identical to that which a delisting petitioner would make for the
underlying waste.  These residues consequently are treated as the
underlying listed waste for delisting purposes.  The statute
likewise takes this position, indicating that soil and debris
that are contaminated with listed spent solvents or dioxin wastes
are subject to the prohibition for these wastes even though these
wastes are not the originally generated waste, but rather are a
residual from management (RCRA section 3004(e)(3)).  It is EPA's
view that all such residues are covered by the existing
prohibitions and treatment standards for the listed hazardous
waste that these residues contain and from which they are
derived.
                               1-44                        Rev. 3

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1.2.8          Transfer of Treatment Standards




     EPA is proposing some treatment standards that are not based

on testing of the treatment technology of the specific waste

subject to the treatment standard.  Instead, the Agency has

determined that the constituents present in the subject waste can

be treated to the same performance levels as those observed in

other wastes for which EPA has previously developed treatment

data.  EPA believes that transferring treatment performance for

use in establishing treatment standards for untested wastes is

valid technically in cases where the untested wastes are

generated from similar industries, similar processing steps, or

have similar waste characteristics affecting performance and

treatment selection.  Transfer of treatment standards to similar

wastes or wastes from similar processing steps requires little

formal analysis.  However, in the case where only the industry is

similar, EPA more closely examines the waste characteristics

prior to concluding that the untested waste constituents can be

treated to levels associated with tested wastes.




     EPA undertakes a two-step analysis when determining whether

wastes generated by different processes within a single industry

can be treated to the same level of performance. First, EPA
                                        *
reviews the available waste characteristic data to identify those

parameters that are expected to affect treatment selection.  EPA

has identified some of the most important constituents and other
                               1-45                         Rev. 3

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parameters needed to select the treatment technology appropriate
for a given waste.  A detailed discussion of each analysis,
including how each parameter was selected for each waste, can be
found in the background document for each waste.

     Second, when an individual analysis suggests that an
untested waste can be treated with the same technology as a waste
for which treatment performance data are already available, EPA
analyzes a more detailed list of constituents that represent some
of the most important waste characteristics that the Agency
believes will affect the performance of the technology.  By
examining and comparing these characteristics, the Agency
determines whether the untested wastes will achieve the same
level of treatment as the tested waste.  Where the Agency
determines that the untested waste is easier to treat than the
tested waste, the treatment standards can be transferred.  A
detailed discussion of this transfer process for each waste can
be found in later sections of this document.

1.3       Variance from the BOAT Treatment Standard

     The Agency recognizes that there may exist unique wastes
that cannot be treated to the level specified as the treatment
standard.  In such a case, a generator or owner/operator may
submit a petition to the Administrator requesting a variance from
the treatment standard.  A particular waste may be significantly
                               1-46                        Rev. 3

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different from the wastes considered in establishing treatability
groups because the waste contains a more complex matrix that
makes it more difficult to treat.  For example, complex mixtures
may be formed when a restricted waste is mixed with other waste
streams by spills or other forms of inadvertent mixing.  As a
result, the treatability of the restricted waste may be altered
such that it cannot meet the applicable treatment standard.

     Variance petitions must demonstrate that the treatment
standard established for a given waste cannot be met.  This
demonstration can be made by showing that attempts to treat the
waste by available technologies were not successful or by
performing appropriate analyses of the waste, including waste
characteristics affecting performance, which demonstrate that the
waste cannot be treated to the specified levels.  Variances will
not be granted based solely on a showing that adequate BDAT
treatment capacity is unavailable.  (Such demonstrations can be
made according to the provisions in Part 268.5 of RCRA for
case-by-case extensions of the effective date.)  The Agency will
consider granting generic petitions provided that representative
data are submitted to support a variance for each facility
covered by the petition.
                               1-47                         Rev. 3

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     Petitioners should submit at least one copy to:

        The Administrator
        U.S. Environmental Protection Agency
        401 M Street, S.W.
        Washington, DC  20460

     An additional copy marked "Treatability Variance" should be

submitted to:

        Chief, Waste Treatment Branch
        Office of Solid Waste (WH-565)
        U.S. Environmental Protection Agency
        401 M Street, S.W.
        Washington, DC  20460
     Petitions containing confidential information should be sent

with only the inner envelope marked "Treatability Variance" and

"Confidential Business Information" and with the contents marked

in accordance with the requirements of 40 CFR Part 2 (41 FR

36902, September 1, 1976, amended by 43 FR 4000).



     The petition should contain the following information:


      (1)  The petitioner's name and address.


      (2)  A statement of the petitioner's interest in the
          proposed action.


      (3)  The name, address, and EPA identification number of the
          facility generating the waste, and the name and
          telephone number of the plant contact.

                                         v
      (4)  The process(es) and feed materials generating the waste
          and an assessment of whether such process(es) or feed
          materials may produce a waste that is not covered by
          the demonstration.
                               1-48                        Rev. 3

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 (5)   A description of the waste sufficient for comparison
      with the waste considered by the Agency in developing
      BOAT,  and an estimate of the average and maximum
      monthly and annual quantities of waste covered by the
      demonstration. (Note:  The petitioner should consult
      the appropriate BOAT background document for
      determining the characteristics of the wastes
      considered in developing treatment standards.)
 (6)   If the waste has been treated,  a description of the
      system used for treating the waste,  including the
      process design and operating conditions.   The petition
      should include the reasons the  treatment  standards are
      not achievable and/or why the petitioner  believes the
      standards are based on inappropriate technology for
      treating the waste.  (Note:  The petitioner should refer
      to the BDAT background document as guidance for
      determining the design and operating parameters that
      the Agency used in developing treatment standards.)
 (7)   A description of the alternative treatment systems
      examined by the petitioner (if any);  a description of
      the treatment system deemed appropriate by the
      petitioner for the waste in question; and, as
      appropriate,  the concentrations in the treatment
      residual or extract of the treatment  residual (i.e.,
      using the TCLP where appropriate for  stabilized metals)
      that can be achieved by applying such treatment to the
      waste.
 (8)   A description of those parameters affecting treatment
      selection and waste characteristics that affect
      performance,  including results of all analyses.  (See
      Section 3.0 for a discussion of waste characteristics
      affecting performance that the Agency has identified
      for the technology representing BDAT.)
 (9)   The dates of the sampling and testing.
(10)   A description of the methodologies and equipment used
      to obtain representative samplevs.
(11)   A description of the sample handling and preparation
      techniques,  including techniques used for extraction,
      containerization,  and preservation of the samples.
                          1-49                         Rev.  3

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    (12)  A description of analytical procedures used including
          QA/QC methods.
     After receiving a petition for a variance, the Administrator
may request any additional information or waste samples that may
be required to evaluate and process the petition.  Additionally,
all petitioners must certify that the information provided to the
Agency is accurate under 40 CFR Part 268.4(b).

     In determining whether a variance will be granted, the
Agency will first look at the design and operation of the
treatment system being used.  If EPA determines that the
technology and operation are consistent with BOAT, the Agency
will evaluate the waste to determine if the waste matrix and/or
physical parameters are such that the BOAT treatment standards
reflect treatment of this waste.  Essentially, this latter
analysis will concern the parameters affecting treatment
selection and waste characteristics affecting performance
parameters.

     In cases where BOAT is based on more than one technology,
the petitioner will need to demonstrate that the treatment
standard cannot be met using any of the technologies, or that
none of the technologies are appropriate,for treatment of the
waste.  After the Agency has made a determination on the
petition, the Agency's findings will be published in the Federal
Register, followed by a 30-day period for public comment.

                               1-50                        Rev. 3

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After review of the public comments, EPA will publish its final



determination in the Federal Register as an amendment to the



treatment standards in 40 CFR Part 268, Subpart D.
                              1-51                         Rev.  3

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        2.   INDUSTRY AFFECTED AND WASTE CHARACTERIZATION


     The previous section provided the background for the

Agency's study of K103 and K104 wastes.  The purpose of this

section is to describe the industry that will be affected by land

disposal restrictions on waste codes K103 and K104, and to

characterize these wastes.  This section includes a description

of the industry affected, the production processes employed in

this industry, and a discussion of how K103 and K104 wastes are

generated by these processes.  The section concludes with a

characterization of the K103 and K104 waste streams, and a

determination of the waste treatability group for these wastes.



     The full list of hazardous waste codes from specific sources

is given in 40 CFR 261.32 (see discussion in Section 1 of this

document).  Within this list, two specific hazardous waste codes

are generated by the aniline/nitrobenzene industry:
     K103:     Process residues from aniline extraction from the
               production of aniline (basis for listing:
               aniline, nitrobenzene, phenylenediamine).

     K104:     Combined wastewater streams generated from
               nitrobenzene/aniline production (basis for
               listing: aniline, benzene, diphenylamine,
               nitrobenzene, phenylenediamine).
     The Agency has determined that these waste codes (K103 and

K104) represent a separate waste treatability group.  This was

established because industry processes are similar; therefore,
                               2-1                         Rev. 3

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the wastes are expected to have similar physical and chemical


characteristics (see Section 1 for a discussion of waste


treatability groups).  In addition, these wastes are frequently


mixed in industry prior to treatment.  As a result, the Agency


has examined the sources of the wastes, applicable treatment


technologies, and treatment performance attainable in order to


support a single regulatory approach for the two wastes.




2.1  Industry Affected and Process Description




     The four digit standard industrial classification  (SIC) code


reported for the aniline/nitrobenzene industry is 2869.  The


Agency estimates that six facilities in the United States are


actively involved in aniline production which could generate


K103.  Four of these facilities are actively co-producing aniline


and nitrobenzene, and could generate K104 waste.




     Information from trade associations provide a geographic


distribution of the number of these facilities across the United

States.  Tables 2-1 and 2-2 present the location of those


facilities which may generate waste codes K103 and K104 in each


state and in each EPA region.  As can be seen in Tables 2-1 and


2-2, these facilities are concentrated in the central and eastern

                                         V
states (EPA Regions III through VI).  Figure 2-1 illustrates this


data plotted on a map of the United States.
                               2-2                         Rev. 3

-------
Table 2-1   Facilities Producing K103 and K104
State (EPA Region)

Louisiana (VI)
Mississippi (IV)
North Carolina  (IV)
Ohio (V)
Texas (VI)
West Virginia (III)
                              Total
Number of Facilities
     1
     1
     1
     1
     1
     1
     6
Reference:  SRI Chemical Economics Handbook, 1985
Table 2-2   Facilities Producing K103 and K104
EPA Rea ion
III
IV
V
VI

Number of Facilities
1
2
1
2
Total 6
Reference;   SRI Chemical Economics Handbook, 1985.




     Nitrobenzene is manufactured by either liquid or vapor phase

nitration of benzene.  The liquid phase nitration process is

reported to be the more prevalent of the two processes used to

manufacture nitrobenzene.  In liquid phase nitration, benzene is

nitrated in a reactor with an aqueous mixture of sulfuric acid

and nitric acid (see Figure 2-2).  Crude .nitrobenzene is formed,

and is separated from the reactants and by-products by a series

of purification steps.
                               2-3
                   Rev. 3

-------
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NITRIC
ACID
                            SODIUM
                            HYDROXIDE
                                                        NITROBENZENE
                                                        PRODUCT
                                                            K103 FROM SEPARATOR
 LIflUID/
 LIBUID
EXTRACTION
                               TO FURTHER
                               HASTEMATER
                               TREATMENT
                                                                          PRODUCT
                                                                          ANILINE
                                                       TO
                                                     INCINERATOR
SOURCE:    DELISTING PETITION FOR WASTE STREAM K104  - COMBINED
           WASTEWATER STREAMS GENERATED FROM NITROBENZENE/ANILINE
           PRODUCTION.   PETITION  NO.  0312.
                               FIGURE 2-2

      GENERATION OF K103  AND K104  FROM NITROBENZENE/ANILINE
  PRODUCTION  (LIQUID  PHASE NITRATION OF  BENZENE  AND LIQUID PHASE
                     REDUCTION  OF NITROBENZENE)
                                  2-5
                                  Rev.  3
-------
     In the initial nitrobenzene purification step,  the product


stream from the reactor enters a separator where it is cooled and


allowed to settle and to separate by gravity into an organic and


an aqueous phase.  The aqueous phase, consisting mainly of


untreated sulfuric and nitric acid, goes to the denitrator where


fresh benzene is added to remove trace amounts of nitric acid.


The benzene and trace amounts of nitrobenzene, formed in the


denitrator, are returned to the nitrobenzene reactor.  The acid


phase from the denitrator is sent to the waste acid stripper for


acid recovery by volatilization.  The recovered acid from the


waste acid stripper is recycled through an acid concentrator to


the reactor.




     The organic phase from the separator, consisting mainly of


nitrobenzene, is washed with water in a prewasher and with


caustic soda in a washer to remove traces of acid.  The washwater


streams from the prewasher and washer are both sent to a


wastewater extractor where nitrobenzene is recovered from the

washwater  (or wastewater).  In the final purification step, the


nitrobenzene stream from the washer is distilled in the


nitrobenzene topping column to produce a high purity nitrobenzene

product.



                                        V
     Aniline is produced by reducing nitrobenzene with hydrogen


in the presence of a catalyst.  The three alternative reduction


processes currently in use are as follows:  catalytic vapor
                               2-6                         Rev. 3
-------
phase, catalytic liquid phase, and dissolving metal (or Bechamp)

process.  Most of the aniline in the United States is reported to

be produced by the catalytic vapor phase and catalytic liquid

phase processes.



     In the catalytic liquid phase process, nitrobenzene is

reduced by hydrogen to form aniline in the presence of a nickel

catalyst in a reactor (see Figure 2-2).   The crude aniline from

the reactor is separated from water and other by-products in a

two-stage gravity decantation process consisting of a crude

aniline separator and a separator.  The water phases from both

separators are combined and sent to the aniline liquid/liquid

extractor which recovers aniline from the residual wastewater

stream.  The aniline stream from the crude aniline separator is

distilled in a rectification column to produce a high purity

aniline product.



     The listed wastes K103 and K104 are generated in the

manufacture of aniline and aniline/nitrobenzene, respectively.

The generation of these wastes is discussed further in Sections

2.1.1 and 2.1.2.



2.1.1  Generation of K103 Waste
                                         «•


     The listed waste K103 is generated in the production of

aniline in both the crude aniline separator and in the
                               2-7                         Rev. 3
-------
aniline/water separator after the rectifier column.  In the crude

aniline separator (see Figure 2-2),  the product stream from the

aniline reactor is cooled and allowed to settle and separate by

gravity into an organic and an aqueous phase.  The aqueous phase,

which is the listed waste K103, is pumped to the aniline

liquid/liquid extractor.




     The bottoms stream from the rectifier column that purifies

the crude aniline enters a purge recovery column which separates

water and aniline by distillation.   The aniline-containing stream

from the purge recovery columns enters a separator where it is

cooled and allowed to settle and separate by gravity into an

organic and an aqueous phase.  The organic phase, consisting

mainly of aniline, is recycled to the aniline reactor.  The


aqueous phase, which is the listed waste K103, is combined with

the aqueous phase from the crude aniline separator and pumped to

the aniline liquid/liquid extractor.  The bottoms from the purge

recovery column are stored in the tars tank and eventually

incinerated.




2.1.2  Generation of K104 Waste




     The listed waste K104 is generated in the production of
                                        V
nitrobenzene at both the prewasher and the washer  (see

Figure 2-2).  In the prewasher, water is used to remove acid from

the nitrobenzene stream coming from the separator by exploiting
                               2-8                         Rev. 3
-------
the relatively high solubility of the acids in water.  An organic

phase, consisting mainly of nitrobenzene, is separated from the

aqueous phase in the prewasher and is sent to the washer.  The

aqueous phase from the prewasher, which is the listed waste K104,

is sent to the nitrobenzene liquid/liquid extractor.




     In the washer, caustic soda is used to neutralize remaining

traces of acid in the nitrobenzene stream from the prewasher.  As

before, organic and aqueous phases are formed by settling and

gravity separation.  Nitrobenzene is removed with the organic

phase from the washer and enters the nitrobenzene topping column.

The aqueous phase from the washer, which is the listed waste

K104, is combined with the aqueous phase from the prewasher and

enters the nitrobenzene liquid/liquid extractor.  Other

wastewater streams from the co-production of nitrobenzene and


aniline are also considered to be K104, if they are not mixed

with the wastewater streams from the prewasher and washer. These

streams include the overhead stream from the waste acid stripper

and the wastewater stream from the aniline liquid/liquid

extractor.




2.2.  Waste Characterization



                                         *
     This section includes all waste characterization data

available to the Agency for the K103 and K104 waste treatability

group.  An estimate of the major constituents which comprise each
                               2-9                         Rev. 3
-------
waste and their approximate concentrations is presented in
Table 2-3.  The percent concentration of each major constituent
in the waste was determined from best estimates based on chemical
analyses.  Table 2-3 shows that the major constituent of both
K103 and K104 is water (at >94.7% and >98.7%, respectively).  The
primary organic BOAT constituent in K103 is aniline, with benzene
and sulfide being the other primary BOAT constituents present
(<1.0%).  The primary organic BOAT constituent in K104 is
nitrobenzene, with benzene and cyanides being the other primary
BOAT constituents present (<1.0%).

     The ranges of BOAT constituents present in each waste and
all other available data concerning waste characterization
parameters obtained from the Onsite Engineering report for E. I.
duPont de Nemours, Beaumont, Texas, are presented by waste code
in Table 2-4.  This table lists the levels of BOAT organics
(volatile and semivolatile), metals, and inorganics present in
K103 and K104 wastes.  Other parameters analyzed in the wastes
include: total dissolved solids, total suspended solids, total
organic carbon, and chemical oxygen demand.  Tables 2-3 and 2-4
together provide a thorough characterization of K103 and K104
wastes.
                               2-10                        Rev. 3
-------
Table 2-3 Major Constituent Composition for K103 and K104 Wastes*
Constituent

Water
Aniline
BDAT Constituents
  (Other than Aniline)
     Total
         K103 Waste
Concentration (Wt. Percent)

             >94.7
               4.3
             100.0%
Constituent

Water
Nitrobenzene
BDAT Constituents
  (Other than Nitrobenzene)
     Total
         K104 Waste
Concentration (Wt. Percent)

             >98.7
               0.3
             100.0
* Percent concentrations presented here were determined from best
  estimates based on chemical analyses.

Reference; Onsite Engineering Report for E. I. duPont de Nemours,
           Beaumont, Texas.  Pages 6 and 8.
                               2-11
                           Rev. 3
-------
                                           TABLE 2-4
                            BOAT CONSTITUENT ANALYSIS AND OTHER DATA
                                              Untreated Waste Conentration Range,  ppm*


    BOAT ORGANICS                          K103                                K104

       Volatile

      4.   Benzene                             32-81                               4.5 - 320

       Semi volatile

     56.   Aniline                    33,000 -  53,000                        <150 -   <300
    101.   2,4-Dinitrophenol          <7,500 - <15,000                         750 - <1,500
    126.   Nitrobenzene                1,900 -   2,800**                     2,200 -  3,900
    142.   Phenol                      1,500 -  <3,000                        <150 -   <300

       BOAT  Metals

    155.   Arsenic                        0.01 - 21                                <0.01
    156.   Barium                         <.001                               .0015 - .017
    159.   Chromium                       <.007                               <.007 - .432
    160.   Copper                         <.006                               <.006 - .012
    161.   Lead                         <.005 - 6                                 <.020
    163.   Nickel                          <.011                               <.011 - .238
    168.   Zinc                            3 - 21                             <.038 - .079

       BOAT  Inorganics

    169.   Total  Cyanides             <0.010 - 0.075                           3.06 - 6.28
    171.   Sulfide                         62 - 89                                 <1.0

       Other Parameters
Total Dissolved Solds
Total Suspended Solids
Total Organic Carbon
Chemical Oxygen Demand
+
8 - 24
33,500 - 36,300
97,800 - 111,000
10,200 - 27,200
21 - 172
1,420 - 2,990
5,290 - 48,200
 * - Values obtained from Onsite  Engineering Report of Treatment Technology Performance for E. I. du Pont
     de Nemours, Inc.,  Beaumont,  Texas.  Tables 6-6 and 6-8.
 + - Total dissolved solids  could not be analyzed since the sample flashed before an analysis could be
     completed. This was due to the amount of organics contained in the sample.
** - Value represents the treated waste from the aniline liquid/liquid extractor.  Nitrobenzene was
     used as a solvent  in the  aniline liquid/liquid extractor.
                                                    2-12                                         Rev.  3
-------
2.3  Determination of Waste Treatability Group







     Fundamental to waste treatment is the concept that the type



of treatment technology used and the level of treatment achieved



depend on the physical and chemical characteristics of the waste.



In cases where EPA believes that wastes represented by different



codes can be treated to similar concentrations using the same



technologies, the Agency combines the codes into one treatability



group.  In particular, the two listed wastes (K103 and K104) from



the production of aniline and nitrobenzene were combined into a



single waste treatability group.







     These two wastes are produced in the aniline/nitrobenzene



industry and are frequently treated together in the industry



using a single waste treatment technology.  Also, the two wastes



have similar physical and chemical characteristics including:



high water content, high BDAT organic levels (benzene and aniline



or nitrobenzene),  relatively low levels of BDAT metals and



inorganics,  and low filterable solids content.  For these



reasons, the Agency believes that the K103 and K104 wastes



represent a separate waste treatability group.
                              2-13                         Rev. 3
-------
        3.  APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES







     The purpose of this section is to describe applicable



treatment technologies for treatment of K103 and K104 wastes that



the Agency has identified as applicable and to describe which of



the applicable technologies the Agency has determined to be



demonstrated.  Included in this section are discussions of those



applicable treatment technologies that have been demonstrated on



a commercial basis.  The technologies which were considered to be



applicable are those which treat organic compounds by



concentration reduction.  Also, this section describes the



performance data available for these technologies.








     The previous section described the industry that will be



affected by the land disposal restrictions on K103 and K104



wastes, and presented a characterization of these wastes.



Analysis of the K103 wastewaters indicates that they primarily



consist of water (94.7 percent) and aniline (4.3 percent).   The



K104 wastewater primarily consists of water (98.7 percent),



nitrobenzene (0.3 percent) and small amounts of cyanides.  The



Agency has identified these treatment technologies which may be



applicable to K103 and K104 because the technologies are designed



to reduce the concentration of organic compounds present in the



untreated waste.  The selection of the treatment technologies



applicable for treating organic compounds and cyanides in K103
                               3-1                         Rev. 3
-------
 and K104 wastewaters is based on information obtained from
engineering site visits and available literature sources.

3.1  Applicable Treatment Technologies

     For K103 and K104 wastewaters, the Agency has identified the
following treatment technologies as being applicable:
liquid/liquid (or solvent) extraction which separates the organic
components from the aqueous components by exploiting the relative
differential or selective solubility of the organic constituents
in a particular solvent; steam stripping, which removes organics
from the liquid phase through volatilization; activated carbon
adsorption which uses carbon granules to selectively remove
organic contaminants by adsorption; and biological treatment
which involves the use of microorganisms to degrade organic
compounds.

     The use of activated carbon adsorption in treating the
wastewaters generates a spent carbon which is nonwastewater.  The
Agency has identified rotary kiln incineration as being an
applicable treatment technology for this nonwastewater form of
K103 and K104.
                               3-2                         Rev. 3
-------
3.2  Demonstrated Treatment Technologies



     i.   Nonwastewaters

     The demonstrated technology that the Agency has identified

for treatment of K103 and K104 nonwastewaters is rotary kiln

incineration.  This technology has not been commercially

demonstrated for the treatment of K103 and K104 nonwastewaters,

but it has been demonstrated for wastes similar to K103 and K104

nonwastewaters.  However, the Agency does not have performance

data for this treatment technology.



     ii.  Wastewaters

     The Agency has determined that all of the applicable

technologies for wastewaters are demonstrated.  The demonstrated

treatment technologies listed above for K103 and K104 generally

are combined to form treatment systems or treatment trains which

are more effective than single technologies alone in removing and

recovering organics from wastewater.  The three treatment

technology systems which are demonstrated or are currently in

commercial use are as follows:


     o    liquid/liquid extraction followed by steam stripping
          and activated carbon adsorption,

     o    steam stripping followed by activated carbon
          adsorption, and

     o    steam stripping followed by biological treatment.
                               3-3                         Rev. 3
-------
     A more detailed discussion of the treatment technology
system for which the Agency has collected performance data is
presented in Sections 3.2.1 through 3.2.3.

3.2.1  Solvent Extraction

     Solvent extraction is a treatment technology used to remove
a constituent from a waste by mixing the waste with a solvent
that is immiscible with the waste and in which the waste
constituent of concern is preferentially soluble.  Solvent
extraction is commonly called liquid extraction or liquid-liquid
extraction.  EPA also uses this term to refer to extraction of
BOAT list organics from a solid waste.  When BOAT list metals are
extracted using acids, EPA uses the term acid leaching.

(1)  Applicability and Use of Solvent Extraction

     Theoretically, solvent extraction has broad applicability in
that it can be used for wastes that have high or low
concentrations of a range of waste characteristics including
total organic carbon, filterable solids, viscosity, and BOAT list
metals content.  The key to its use is whether the BOAT
constituents can be extracted from the waste matrix containing
the constituents of concern.  For a waste matrix with high
filterable solids this would mean that the solids could be land
disposed following solvent extraction.  For a predominately


                               3-4                         Rev. 3
-------
liquid waste matrix with low filterable solids, the extracted



liquid (referred to as the raffinate)  could be reused.  Solvent



extraction can seldom be used without additional treatment



(e.g., incineration) of the extract; however, some industries may



be able to recycle the solvent stream contaminated with the BOAT



constituents back to the process.








(2)  Underlying Principles of Operation







     For solvent extraction to occur,  the BDAT constituents of



concern in the waste stream must be preferentially soluble in the



solvent and the solvent must be essentially immiscible with the



waste stream.  In theory, the degree of separation that can be



achieved is provided by the selectivity value; this value is the



ratio of the equilibrium concentration of the constituent in the



solvent to the equilibrium concentration of the constituent in



the waste.








     The solvent and waste stream are mixed to allow mass



transfer of the constituent(s) from the waste stream to the



solvent.   The solvent and waste stream are then allowed to



separate under quiescent conditions.  The solvent solution,



containing the extracted contaminant is called the extract.  The



extracted waste stream with the contaminants removed is called



the raffinate.  The simplest extraction system comprises three



components:  (1) the solute, or the contaminant to be extracted;









                               3-5                         Rev. 3
-------
(2)  the solvent; and (3) the nonsolute portion of the waste

stream.  For simple extractions, solute passes from the waste

stream to the solvent phase.  A density difference exists between

the solvent and waste stream phases.  The extract can be either

the heavy phase or the light phase.




(3)   Physical Description of a Solvent Extraction Process




     The simplest method of extraction is a single stage system.

The solvent and waste stream are brought together; clean effluent

and solvent are recovered without further extraction.  The clean

effluent is referred to as the raffinate, and the solvent

containing the constituents that were removed from the waste

stream are known as the extract.  The amount of solute extracted

is fixed by equilibrium relations and the quantity of solvent

used.  Single stage extraction is the least effective extraction

system.




     Another method of extraction is simple multistage contact

extraction.  In this system, the total quantity of solvent to be

used is divided into several portions.  The waste stream is

contacted with each of these portions of fresh solvent in a

series of successive steps or stages.  Raffinate from the first
                                         V
extraction stage is contacted with fresh solvent in a second

stage, and so on.
                               3-6                         Rev. 3
-------
     In counter-current,  multistage contact, fresh solvent and the

waste stream enter at opposite ends of a series of extraction

stages.  Extract and raffinate layers pass continuously and

countercurrently from stage to stage through the system.




     In order to achieve a reasonable approximation of phase

equilibrium, solvent extraction requires the intimate contacting

of the phases.  Several types of extraction systems are used for

contact and separation;  two of these, mixer-settler systems and

column contactors, are discussed below.




     i.  Mixer-Settler Systems

     Mixer-settler systems are comprised of a mixing chamber for

phase dispersion, followed by a settling chamber for phase

separation.  The vessels may be either vertical or horizontal.

Dispersion in the mixing chamber occurs by pump circulation,

nonmechanical in-line mixing, air agitation, or mechanical

stirring.  In a two-stage mixer-settler system the dispersed

phase separates in a horizontal settler.  The extract from the

second settler is recycled to the first settler (see Figure 3-1).

Extract properties such as density or specific constituent

concentration may be monitored to determine when the extract must

be sent to solvent recovery and fresh or regenerated solvent
                                         *>
added to the system.  Mixer-settler systems can handle solids or

highly viscous liquids.   Design scaleup is reliable, and

mixer-settlers can handle difficult dispersion systems.  Intense





                               3-7                         Rev. 3
-------
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agitation to provide high rates of inass transfer can produce

solvent-feed dispersions that are difficult to separate into

distinct phases.




     ii.  Column Contactors

     Packed and sieve-tray are two different types of column

contactors that do not require mechanical agitation.  Figure 3-2

presents schematics of the two types of extraction columns.




     A packed extractor contains packing materials, such as

saddles, rings, or structured packings of gauze or mesh.  Mass

transfer of the solute to the extract is promoted because of

breakup and distortion of the dispersed phase as it contacts the

packing.




     The sieve-tray extractor is similar to a sieve-tray column

used in distillation.  Tray perforations result in the formation

of liquid droplets to aid the mass transfer process.  The

improved transfer is accomplished by the fact that the droplets

allow for more intimate contact between extract and raffinate.




(4)  Waste Characteristics Affecting Performance



                                         V
     In determining whether solvent extraction is likely to

achieve the same level of performance on an untested waste as a

previously tested waste, the Agency will focus on the waste





                               3-9                         Rev. 3
-------
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characteristics that provide an estimate of the selectivity value



previously described.  EPA believes that the selectivity value



can best be estimated by analytically measuring the partitioning



coefficients of the waste constituents of concern and the



solubility of the waste matrix in the extraction solvent.



Accordingly, EPA will use partitioning coefficients and



solubility of the waste matrix as surrogates for the selectivity



value in making decisions regarding transfer of treatment



standards.







     For the liquid/liquid extraction system, the WCAPs are the



relative solubilities which is a measure of the partitioning



coefficient, of the various waste constituents in water and in



nitrobenzene.  The primary organic constituents of K103 and K104



(benzene, aniline, nitrobenzene, phenol, and 2,4-dinitrophenol),



along with cyanides, are all soluble in nitrobenzene at 40°C.



Phenol and cyanides are soluble in water at 40°C, while benzene,



aniline, and nitrobenzene are relatively insoluble in water



(0.137 g/100 g H20saturated solution at 54.5°C).  It should also



be noted that the density of nitrobenzene relative to water is



1.205 at 4°C.
                              3-11                         Rev. 3
-------
(5)   Design and Operating Parameters







     EPA's analysis of whether a solvent extraction system is



well designed will focus on whether the BOAT list constituents



are likely to be effectively separated from the waste.  The



particular design and operating parameters to be evaluated are:



(1)  the selection of a solvent, (2) equilibrium data, (3)



temperature and pH, (4) mixing, and (5) settling time.







     (1)  The selection of a solvent.   In assessing the design of



a solvent extraction system, the most important aspect to



evaluate is the solvent used and the basis on which the



particular solvent was selected.  Solvent selection is important



because, as indicated previously, different waste constituents of



concern will have different solubilities in various solvents, and



it is the extent to which the waste constituents



are preferentially soluble in the selected solvent that



determines the effectiveness of this technology.  In addition to



this information, EPA would also want to review any empirical



extraction data used to design the system.







     (2)  Equilibrium Data.  For solvent extraction systems that



are operated in a continuous mode, the extraction process will



generally be conducted using a series of equilibrium stages as



discussed previously.  The number of equilibrium stages and the



associated flow rates of the waste and solvent will be based on
                               3-12                        Rev. 3
-------
empirical equilibrium data.  EPA will evaluate these data as part



of assessing the design of the system.







     (3)   Temperature and pH.  Temperature and pH changes can



affect equilibrium conditions and, consequently, the performance



of the extraction system.  Thus, EPA would attempt to monitor and



record these values on a continuous basis.







     (4)   Mixing.  For mixer-settler type extraction processes,



mixing determines the amount of contact between the two



immiscible phases and, accordingly, the degree of mass transfer



of the constituents to be extracted.  EPA would thus want to know



the type of mixers used and the basis for determining that this



system would provide sufficient mixing.







     (5)   Settling Time.  For batch systems, adequate settling



time must be allowed to ensure that separation of the phases has



been completed.  Accordingly, in assessing the design of a



system, EPA would want to know settling time allowed and the



basis for selection.
                               3-13                         Rev. 3
-------
3.2.2  Steam Stripping





   Steam stripping is a technology which can separate more



volatile materials from less volatile materials by a process of



vaporization and condensation.  As such, it is a type of



distillation process.







(1)     Applicability and Use of Technology








   Steam stripping is applicable to wastewaters that contain BOAT



organics that are sufficiently volatile such that they can be



removed by the application of steam.  Waste parameters affecting



treatment selection are filterable solids, total organic carbon



(TOC), and the presence of BDAT organics that are either not



volatile or only minimally volatile.







(2)     Underlying Principles of Operation







   The basic principle of operation for steam stripping is the



volatilization of hazardous constituents through the application



of heat.  The constituents that are volatilized are then



condensed and either reused or further treated by liquid



injection incineration.








   An integral part of the theory of steam stripping is the



principle of vapor-liquid equilibrium.  When a liquid mixture of



two or more components is heated, a vapor phase is created above








                               3-14                         Rev. 3
-------
the liquid phase.  The vapor phase will be more concentrated in



the constituents having the higher vapor pressure.  If the vapor



phase above the liquid phase is cooled to yield a condensate, a



partial separation of the components results.  The degree of



separation would depend on the relative differences in the vapor



pressures of the constituents; the larger the difference in the



vapor pressure, the easier the separation can be accomplished.







   If the difference between the vapor pressure is extremely



large, a single separation cycle or single equilibrium stage of



vaporization and condensation may achieve a significant



separation of the constituents.  If the difference between the



vapor pressures are small, then multiple equilibrium stages are



needed to achieve effective separation.  In practice, the



multiple equilibrium stages are obtained by stacking trays or



placing packing into a column.  The vapor phase from a tray rises



to the tray above it and the liquid phase falls to the tray below



it.  Essentially, each tray represents one equilibrium stage.  In



a packed steam stripping column, the individual equilibrium



stages are not discernible, but the number of equivalent trays



can be calculated from mathematical relationships.







   The vapor liquid equilibrium is expressed as relative



volatility or the ratio of the vapor to liquid concentration for



a constituent divided by the ratio of the vapor to liquid



concentration of the other constituent.  The relative volatility
                               3-15                         Rev. 3
-------
is a direct measure of the ease of separation.   If the numerical


value is 1, then separation is impossible because the


constituents have the same concentrations in the vapor and liquid


phases.  Separation becomes easier as the value of the relative


volatility becomes increasingly greater than unity.




(3)     Physical Description of the Process




   A steam stripping unit consists of a boiler, a stripping


section, a condenser, and a collection tank as shown by Figure


3-3.  The boiler provides the heat required to vaporize the


liquid fraction of the waste.  The stripping section is composed


of a set of trays or packing in a vertical column.  The feed


enters at the top.




   The stripping process uses multiple equilibrium stages, with


the initial waste mixture entering the uppermost equilibrium


stage.  The boiler is located below the lowermost equilibrium


stage so that vapor generated moves upward in the column coming


into contact with the falling liquid.  As the vapor comes into


contact with the liquid at each stage, the more volatile


components are removed or "stripped" from the liquid by the vapor


phase.  The concentration of the emerging vapor is slightly

                                         V
enriched (as it is in equilibrium with the incoming liquid), and


the liquid exiting the bottom of the boiler ("bottoms") is


considerably enriched in the lower vapor pressure constituent(s).
                               3-16                         Rev. 3
-------
HASTE
INFLUENT
                                VENT OF
                          NON-CONDENSED VAPORS
                                  A
                                          CONDENSER
TREATED
EFFLUENT
RECIEVER

RECOVERED
SOLVENT  FOR
REUSE OR
TREATMENT
                 FIGURE  3-3
              STEAM STRIPPING
                         3-17
     Rev. 3
-------
The process of stripping is very effective for wastewaters where


the relative volatilities are large between the organics of


concern and wastewater.  Steam stripping is used to strip the


organic volatiles from wastewater.  The water effluent from the


bottom of the stripper is reduced in organic content, but in some


circumstances may require additional treatment, such as carbon


adsorption or biological treatment.  The steam and organic vapors


leaving the top of the column are condensed.  Organics in the


condensate that form a separate phase in water usually can be


separated and recovered or disposed of in a liquid injection


incinerator.  After separation the aqueous condensate is usually


recycled to the stripper.




(4)     Waste Characteristics Affecting Performance




   In determining whether steam stripping is likely to achieve


the same level of performance on an untested waste as a


previously tested waste, EPA will focus on the following

characteristics:  boiling point, total dissolved solids, total


dissolved volatile solids, and oil and grease.  EPA recognizes


these characteristics have some limitations in assessing transfer


of performance; nevertheless, the Agency believes that they


provide the best possible indicator of the preferred waste

                                         »
characteristic analysis, i.e., relative volatility.  Below is a


discussion of relative volatility, as well as, EPA's rationale


for evaluating the above described waste characteristics in
                               3-18                         Rev. 3
-------
determining transfer of treatment performance.



   As discussed earlier, the term relative volatility ( OC )

refers to the ease with which a substance present in a solid or

liquid waste will vaporize from that waste upon application of

heat from an external source.  Hence, it bears a relationship to

the equilibrium vapor pressure of the substance.
   For an ideal  binary mixture,  the relative volatility ( o< )  is

expressed as:
                  Ki    YiXi
             -    SJ  = Y^7
where K. and K. are equilibrium concentrations for components i

and j respectively, Y is the mole fraction of the component in

the vapor and X is the mole fraction of the component in the

liquid.
*
   The term "ideal" refers to whether the vapor pressures of the
   two components can be linearly related to their respective
   compositions in the liquid phase; this,, is known as Raoult's
   law.  In general, binary solutions at low pressures follow
   this law and are, therefore,  "ideal"; most mixtures do not.
                              3-19                         Rev.  3
-------
     For non-ideal binary mixtures, the relative volatility (
is expressed as:
            (   = --  =  -- x            x
                  KJ      xi    fi,v/   Xj    fjjV
where f is the fugacity.  The term "fugacity" is a conveniently
defined thermodynamic term to account for departures from ideal
behavior of the gas and liquid; it can only be determined
empirically.

     EPA recognizes that the relative volatilities can not be
measured or calculated directly for the types of wastes generally
treated by steam stripping even if these wastes behaved in an
ideal manner.  Determining relative volatilities is further
complicated by the fact that the relative volatility changes as
the temperature conditions change throughout the steam stripper.
Accordingly, EPA will use the following surrogates:  boiling
point of the constituent, oil and grease content, total dissolved
inorganic solids, and total dissolved volatile solids.

     For a given pressure and temperature, compounds with lower
boiling points will have higher vapor pressures.  Therefore, in
the case of wastewaters containing low concentrations of organics
where relative volatility is effectively a comparison of vapor
pressures, the ratio of boiling points of the untested and tested
constituents will indicate whether the untested waste can be
treated to the same degree as the tested constituent.  Boiling
                               3-20                        Rev. 3
-------
point alone would not account for any non-ideal behavior of the



solution.  Accordingly, EPA will examine the concentrations of



oil and grease, total dissolved solids, and total dissolved



volatile solids.  All of these characteristics affect the partial



pressures of the individual organic constituents of concern as



well as the solubility.  Accordingly, these characteristics will



affect relative volatility of a constituent and, hence, the



ability of the constituent to be treated using steam stripping.







     The WCAPs for the steam stripper are the vapor pressures of



the various constituents in the waste.  The higher the vapor



pressure, the more easily stripped.  At 40°C, benzene has a vapor



pressure of 182.7 mm Hg, aniline has a vapor pressure of 2.90 mm



Hg, and phenol has a vapor pressure of 2.02 mm Hg.  Nitrobenzene



has a vapor pressure of 1 mm Hg at 44.4°C, and 2,4-dinitrophenol



has a vapor pressure of 1 mm Hg at 49.3°C.  The cyanides present



are primarily solid salts, and hence have low vapor pressures or



decompose upon heating.  There are no known azeotropes among the



constituents of these wastes, and there is no known



polymerization potential upon heating these wastes.







(5)  Design and Operating Parameters







     EPA's analysis of whether a steam stripping system is well



designed will focus on the degree of separation the system is



designed to achieve and the controls installed to maintain the
                               3-21                         Rev. 3
-------
proper operating conditions.  The specific parameters are

presented below.




     (1)  Treated and Untreated Concentrations.  In determining

whether to sample a particular steam stripper as a candidate for

BOAT, EPA will pay close attention to the treated design

concentration of the unit to ensure that it is consistent with

best demonstrated practice.  This evaluation is important in that

a treatment system will usually not perform its design. The

various untreated waste characteristics that affect performance

are important to know, because operation of the system with

untreated waste concentrations in excess of initial design

conditions can easily result in poor performance of the treatment

unit.  In evaluating the performance of a steam stripper, EPA

would want data on the untreated waste characteristics to ensure

that they conformed with design specifications.




     (2)  Vapor-Liquid Equilibrium Data.  The vapor liquid

equilibrium data are determined in laboratory tests unless

already available.  The use of these data are required for

several reasons.  First, they are used to calculate the number of

theoretical stages required to achieve the desire separation.

Using the theoretical number of stages, the actual number of
                                         V
stages can then be determined through the use of empirical tray

efficiency data supplied by an equipment manufacturer.
                               3-22                         Rev. 3
-------
     Secondly, the vapor liquid equilibrium data are used to

determine the liquid and vapor flow rates that ensure sufficient

contact between the liquid and vapor streams.  These rates are,

in turn, used to determine the column diameter.




     (3)  Column Temperature and Pressure.  These parameters are

integrally related to the vapor liquid equilibrium conditions.

Column temperature design include performing a heat balance

around the steam stripping unit, accounting for the heat removed


in the condenser, heat input in the feed, heat input from steam

injectors and heat loss from the column.  Column pressure

influences the boiling point of the liquid.  For example, the

column temperature required to achieve the desired separation can

be reduced by operating the system under vacuum.  During


treatment, it is important to continuously monitor these

parameters to ensure that the system is operated at design

conditions.




     (4)  Column Internals.  Column internals are designed to

accommodate the physical and chemical properties of the

wastewater to be stripped.  Two types of internals may be used in

steam stripping:  trays or packing.  Tray types include bubble

cap, sieve, valve and turbo-grid.  Trays have several advantages
                                         *•
over packing.  Trays are less susceptible to blockage by solids,

they have a lower capital cost for large diameter columns

(greater than or equal to 3 feet), and they accommodate a wider
                               3-23                         Rev. 3
-------
range of liquid and vapor flow rates.  Compared to trays, packing

has the advantages of having a lower pressure drop per

theoretical stage, being more resistant to corrosive materials,

having a lower capital cost for small diameter column (less than

3 feet), and finally being less susceptible to foaming because of

a more uniform flow distribution.




3.2.3   Carbon Adsorption




     Adsorption with activated carbon is an important separation

method for removing organics and some other dissolved materials

from liquids.  It occurs when the surface of the activated carbon

attracts the ions or molecules of the organic or dissolved solid

to form a layer on the carbon surface and accumulate in its

pores.




 (1)  Applicability and Use of Technology




     Activated carbon treatment is used to remove dissolved

organic pollutants from aqueous streams.  To a lesser extent it

also is used to remove dissolved heavy metal and other inorganic

contaminants.  Inorganics are usually not very adsorbable, but

there are some exceptions (e.g., molybdates, gold chloride,
                                         v
mercuric chloride, silver salts and iodine).  The most effective

metals removal occurs with metal/inorganic complexes, or metal

organic complexes.





                               3-24                        Rev. 3
-------
     Activated carbon treatment is not selective in the organic



contaminants it will remove.  Hence, all organics will compete



for system capacity, including organics that are not necessary to



remove.  In some systems (downflow granular activated carbon



beds), suspended solids over 50 mg/1 cannot be tolerated and must



be removed prior to activated carbon treatment.  Activated carbon



is frequently applied as a final polishing mechanism following



other treatment technologies (e.g., biological treatment).







     These waste component separations most commonly occur in



industries manufacturing organic chemicals, inorganic chemicals,



dyes and pigments, insecticides, refineries, textiles,



explosives, food, tobacco,  leather, primary metals, fabricated



metals, Pharmaceuticals, and plastics.








(2)  Underlying Principles of Operation







     Activated carbon treatment is an application of the



principle of adsorption.  Adsorption is the mass transfer of a



molecule from a liquid or gas into a solid surface.







     Activated carbon is manufactured in such a way as to produce



extremely porous carbon particles, whose internal surface area is



very large (500 to 1400 square meters per gram of carbon).  This



porous structure, through chemical and physical forces, attracts



and holds (adsorbs) organic molecules as well as certain
                               3-25                         Rev. 3
-------
inorganic molecules.  It is not unusual for activated carbon to

adsorb from aqueous solution 0.15 grams of an organic contaminant

per gram of carbon, though 0.10 gram/gram is probably a more

realistic general estimate.  The principal factor that affects

carbon adsorption is the chemical affinity between the carbon and

the organic compound.  Other characteristics such as solubility,

temperature, pH, type of activated carbon used and presence of

other organics also influence the effectiveness of carbon

adsorption.




     The effectiveness of adsorption generally improves with

increasing contact time.  Exceptions to this rule include

chemical compounds that are not preferentially adsorbed onto the

carbon surface.  These compounds can be adsorbed from adsorption

sites in favor of compounds that have a higher affinity for the

carbon over a longer contact time.




     Once the contaminants/impurities have been removed from the

waste stream onto the carbon, two options are available.  The

activated carbon can be (1) disposed of by approved methods

(usually incineration) or  (2) regenerated by thermal or chemical

methods for further use.



                                         V
     There is a loss of performance with each regeneration step;

therefore, the activity is never restored to its original level.

The number of times that the carbon can be regenerated is





                               3-26                         Rev. 3
-------
determined by the extent of physical erosion and the loss of



adsorptive capacity.  Isotherm tests on the regenerated carbon



can be used to determine adsorptive capacity, thereby aiding in



the prediction of the number of times the carbon can be



regenerated.







(3)  Waste Characteristics Affecting Performance








     The waste characteristics that will affect an activated



carbon system's performance are as follows:  (i) type of organic



contaminants, (ii) concentration of contaminants, and (iii)



suspended solids, grease and oil concentration.







     At first, it might appear that pH and temperature would be



significant factors that would affect adsorption.  Polarity of



some organic compounds are affected by pH, and polarity changes



influence adsorption.  Particularly with heavy metals, the



activated carbon must have the proper pH to achieve satisfactory



removal.  Temperature becomes a significant factor when they



become high enough to desorb contaminants from activated carbon



(usually over 100°C).  However, these factors are considered to



be easily controlled during the actual process and, as such, are



not major hindrances to efficient adsorption.
                              3-27                         Rev. 3
-------
     i.  Type of Organic Contaminants

     All organic molecules can be adsorbed by activated carbon to
some degree.  Generally, adsorption will increase with molecular
weight until the particle size becomes too large for carbon pore
size.  However, the activated carbon usually has a greater
affinity for aromatic compounds than straight chain compounds.
Nonpolar compounds are usually easily adsorbed, whereas polar
ones are not.  Halogenated organic compounds (HOCs),  if aromatic
(such as PCBs), are readily adsorbed.  Finally, it has been
demonstrated in practice that adsorption will increase with
decreasing solubility.

     For the carbon adsorption system, the WCAPs are the
molecular weights of the constituents present.  The molecular
weights of the major constituents in the waste are as follows:
78.12 for benzene, 123.11 for nitrobenzene, 93.13 for aniline,
94.11 for phenol, and 184.11 for 2,4-dinitrophenol.  The cyanides
present are thought to be a mixture of complex organic and
inorganic cyanide compounds, and therefore the molecular weight
cannot be determined.  Other important characteristics of the
waste for the carbon adsorption unit are the total organic carbon
content (which is 444 mg/1) and the total suspended solids
content (which is 196 mg/1).  The amount of oil and grease in the
waste is not known.
                               3-28                         Rev. 3
-------
     ii.  Concentration of Contaminants







     In actual practice this process becomes ineffective at



concentrations exceeding a few thousand mg/1.  The carbon will



adsorb concentrated contaminants so fast that carbon consumption



will become excessive, and frequent disposal and/or regeneration



of carbon is likely to become a greater problem than removal of



the organic materials from the waste stream.  For excessively



concentrated waste streams, other organic compound destruction



techniques would probably be more appropriated (e.g.,



incineration or reuse as a fuel).








     iii.  Suspended Solids and Grease and Oil Concentration







     In powdered activated carbon (PAC) systems,  suspended solids



and grease concentrations in the wastewater stream have no



effect, since they are removed from the waste along with the



spent PAC.  However, in nonfluidized granular activated carbon



(GAC) systems (see Section 4.4 for a description of these



systems), the column of GAC acts as a filter for suspended



particles and greases.  It will eventually become plugged or



binded with solids, or coated with grease and oils, and not be



able to sustain the flow of wastewater.  Consequently, the more



suspended solids or grease and oils in the GAC column influent,



the sooner it must be backwashed, hence slowing the dissolved



organic compound removal rate.
                               3-29                         Rev. 3
-------
(4)   Physical Description of the Process

     Specific designs will depend on the waste stream to be
treated and the type of end product desired.  However, a few
examples will provide some idea of how these systems work.

     i.  Systems using PAC.  PAC can be easily used in exiting
equipment such as tanks, filtration or settling apparatus.  Since
it is a fine powder, it is usually put directly into the waste
stream.  It needs lower contact times than GAG because it adsorbs
contaminants more quickly.  PAC usually has less adsorption
capacity than GAC, so more is required.  A few treatment systems
are described below.

        (a)  Batch system.  The incoming waste stream is
thoroughly stirred with the PAC, usually with some type of
mechanical agitator.  The stirring time (contact time) is usually
20 to 30 minutes in most cases.  After adsorption equilibrium is
reached, the mixture is settled and/or filtered to separate the
PAC from the wastewater.  This procedure can be separated to
increase filtrate clarity.

        (b)  Continuous system.  In a continuous system both the
waste liquid and carbon slurry enter mixing tanks simultaneously
and continuously.  Continuous settling and/or filtration again
follow the mixing.


                               3-30                        Rev. 3
-------
     ii. Systems using GAC.  In GAC systems the carbon is packed



in columns and the liquid is passed through a bed of the carbon.



The liquid flow can be either up or down through the vertical



column.  Figure 3-4 shows some common systems.







     Typically, the wastewater to be treated is passed downward



through a stationary bed of carbon.  The constituent to be



removed is adsorbed most rapidly and effectively by the upper few



layers of fresh carbon during the initial stages of operation.



These upper layers are in contact with the wastewater at its



highest concentration level.  The small amounts of target



constituent that escape adsorption in the first few layers of the



activated carbon are removed from solution in the lower or



downstream portion of the bed.  Initially, none of the



constituent to be removed escapes form the adsorbent.







     As the liquid flows down the column, the adsorption capacity



is reached in the top layers, the adsorption zone starts moving



down the column.  As the adsorption zone moves near the end of



the bed, the concentration in the effluent rapidly approaches the



influent concentration.  This point in the operation is referred



to as breakthrough.  A breakthrough curve (Figure 3-5) is the



plot of the ratio of effluent to influent concentrations versus



time of operation.  At breakthrough the bed is exhausted and



little additional removal of the constituent will occur.  At this



point, the carbon must be replaced or regenerated.
                              3-31                         Rev. 3
-------
    IN
                    OUT
    ••"••
    —:..
    •.:.••.•
                        ••-•5.;
                            OUT
       DOMNFLOH IN SERIES
  IN
                            OUT
                                            Ft£vfM
                                           *" V* «V


                                           &."•:"
                                         IN
                • •*•**••

                -liSr:
                                                                   OUT
      COCURRENT  IN PARALLEL
COUNTERCURHENT- EXPANDED  IN SERIES
SOURCE- RIZZO AND SHEPHARD 1967
         FIGURE 3-4  TYPICAL  COLUMN  CONFIGURATIONS
                                    3-32
                              Rev. 3
-------
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                                          3-33
                                 Rev.  3
-------
(5)  Design and Operating Parameters







     Design Parameters







     The system design must account for three parameters that



affect the ability of activated carbon to adsorb contaminants: i)



contact time, ii) carbon particle type and size, and iii)



wastewater flow rate.








     i.  Contact time.  For both PAC/GAC systems, contact time



must be determined by testing individual wastes with different



activated carbon samples.  Once contact time is determine for



adequate removal of contaminants, tank sizing is the next step



and it will depend on waste flow rate.







     ii.  Carbon particle type and size.  Activated carbon is



made from a variety of substances (e.g., coal, wood), ground to



many different sizes, and manufactured with "customized" pore



sizes.  A range of surface areas and individual pore sizes will



determine the carbon's adsorptive capacity.  Bench testing is



recommended to determine the most effective activated carbon



product for a particular waste stream and desired effluent.







     iii.  Wastewater flow rate.  GAC systems are designed for



upflow or downflow operation.  For both types, there are



practical limits to the liquid velocity.  Once the velocity and










                               3-34                         Rev.  3
-------
contact time are determined, the bed cross-section and depth are

sized to meet these requirements.




     Operating Parameters




     A number of parameters must be maintained during operation

to ensure that the adsorption system adheres to the design

specifications.  These are:  (i) waste liquid concentration, (ii)

suspended oils and solids, and  (iii) contact time.




     i.  Waste liquid concentration.  In GAC systems, the

concentration has a direct effect on the operation of an

adsorption system because if the concentration is significantly

higher than the design concentration, column breakthrough will

occur quickly and excessive regeneration will be required.

Conversely, if, during the operation of a column, the waste

liquid concentration decreases significantly, previously adsorbed

molecules can be desorbed from the carbon and be discharged in

the effluent stream.  Additionally, changes in the waste

composition can cause previously adsorbed molecules to be

desorbed and replaced by molecules of a different constituent if

the new constituent has a higher affinity for the carbon surface.

These types of situations can lead to effluent concentrations for
                                         v-
a particular waste constituent that are higher than influent

concentrations.  Waste liquid concentration has a lesser effect

on PAC systems because the PAC is removed as it is spent.
                              3-35                         Rev. 3
-------
Desorption is not a problem.  However,  if the concentration

increases significantly over the design concentrations, excessive

quantities of PAC may be required.   In any case, the effluent

must be monitored for breakthrough of contaminants.




     ii.  Suspended oils and solids.  Suspended oils and solids

are not usually a problem with PAC systems.  However, in GAC

systems, oils and suspended solids in the waste will eventually

plug the column.  If the concentration of solids is significant

(typically greater than 200 mg/1),  the waste will need to be

pretreated to remove them.  In any case, suspended solids and

greases present in the GAC column influent will necessitate

backwashing and/or column cleaning.  The need for such cleaning

can be detected with pressure gauges which monitor the degree of

plugging.




     iii.  Contact time.  Contact time requirements vary with the

type of system but must be maintained within design

specifications.  Typical contact times vary between 300 and 100

minutes for GAC systems, and are somewhat lower for PAC systems.

For GAC systems, typical downflow rates are between 20 and 330

1/min m2 of bed area.  A typical upflow rate is 610 1/min m2 of

bed area, unless the bed is fluidized in which case higher
                                         V
velocities are necessary.  Contact time is monitored by measuring

wastewater flow rate, since system volume is predetermined.
                               3-36                        Rev. 3
-------
3.2.4  Incineration







     This section addresses the commonly used incineration



technologies: Liquid injection, rotary kiln, fluidized bed



incineration, and fixed hearth.  A discussion is provided



regarding the applicability of these technologies, the underlying



principles of operation, a technology description, waste



characteristics that affect performance, and finally important



design and operating parameters.  As appropriate the subsections



are divided by type of incineration unit.







(1)  Applicability and Use of this Technology







     i.  Liquid Infection



     Liquid injection is applicable to wastes that have viscosity



values sufficiently low so that the waste can be atomized in the



combustion chamber.  A range of literature maximum viscosity



values are reported with the low being 100 SSU and the high being



10,000 SSU.  It is important to note that viscosity is



temperature dependent so that while liquid injection may not be



applicable to a waste at ambient conditions, it may be applicable



when the waste is heated.  Other factors that affect the use of



liquid injection are particle size and the presence of suspended



solids.  Both of these waste parameters can cause plugging of the



burner nozzle.
                               3-37                         Rev. 3
-------
     ii.  Rotary Kiln/ Fluidized Bed/ Fixed Hearth

     These incineration technologies are applicable to a wide

range of hazardous wastes.  They can be used on wastes that

contain high or low total organic content,  high or low filterable

solids, various viscosity ranges, and a range of other waste

parameters.  EPA has not found these technologies to be

demonstrated on wastes that are comprised essentially of metals

with low organic concentrations.  In addition, the Agency expects

that some of the high metal content wastes may not be compatible

with existing and future air emission limits without emission

controls far more extensive than currently practiced.




(2)  Underlying Principles of Operation




     i.  Liquid Injection

     The basic operating principle of this incineration

technology is that incoming liquid wastes are volatilized and

then additional heat is supplied to the waste to destabilize the

chemical bonds.  Once the chemical bonds are broken, these

constituents react with oxygen to form carbon dioxide and water

vapor.  The energy needed to destabilize the bonds is referred to

as the energy of activation.



                                         V
     ii.  Rotary Kiln and Fixed Hearth

     There are two distinct principles of operation for these

incineration technologies, one for each of the chambers involved.





                               3-38                         Rev. 3
-------
In the primary chamber, energy, in the form of heat, is



transferred to the waste to achieve volatilization of the various



organic waste constituents.  During this volatilization process



some of the organic constituents will oxidize to CO  and water
                                                   £t


vapor.  In the secondary chamber, additional heat is supplied to



overcome the energy requirements needed to destabilize the



chemical bonds and allow the constituents to react with excess



oxygen to form carbon dioxide and water vapor.  The principle of



operation for the secondary chamber is similar to liquid



injection.








     iii.  Fluidized Bed



     The principle of operation for this incinerator technology



is somewhat different than for rotary kiln and fixed hearth



incineration relative to the functions of the primary and



secondary chambers.  In fluidized bed, the purpose of the primary



chamber is not only to volatilize the wastes but also to



essentially combust the waste.  Destruction of the waste organics



can be accomplished to a better degree in the primary chamber of



this technology than for rotary kiln and fixed hearth because of



1) improved heat transfer from fluidization of the waste using



forced air and 2) the fact that the fluidization process provides



sufficient oxygen and turbulence to convert the organics to


                                         V

carbon dioxide and water vapor.  The secondary chamber (referred



to as the freeboard) generally does not have an afterburner;



however, additional time is provided for conversion of the
                               3-39                         Rev. 3
-------
organic constituents to carbon dioxide, water vapor, and



hydrochloric acid if chlorine is present in the waste.



(3)  Description of Incineration Technologies








     i.  Liquid Injection



     The liquid injection system is capable of incinerating a



wide range of gases and liquids.  The combustion system has a



simple design with virtually no moving parts.  A burner or nozzle



atomizes the liquid waste and injects it into the combustion



chamber where it burns in the presence of air or oxygen.  A



forced draft system supplies the combustion chamber with air to



provide oxygen for combustion and turbulence for mixing.  The



combustion chamber is usually a cylinder lined with refractory



(i.e., heat resistant) brick and can be fired horizontally,



vertically upward, or vertically downward.  Figure 3-6



illustrates a liquid injection incineration system.








     ii.  Rotary Kiln



     A rotary kiln is a slowly rotating, refractory-lined



cylinder that is mounted at a slight incline from the horizontal



(see Figure 3-7).  Solid wastes enter at the high end of the



kiln, and liquid or gaseous wastes enter through atomizing



nozzles in the kiln or afterburner section.  Rotation of the kiln



exposes the solids to the heat, vaporizes them, and allows them



to combust by mixing with air.  The rotation also causes the ash



to move to the lower end of the kiln where it can be removed.
                               3-40                        Rev. 3
-------
                                   LJ
                                   o:
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                                                 GAS TO
                                               AIR POLLUTION
                                                 CONTROL
              AUXILIARY
               FUEL
SOLID WASTE
  INFLUENT
              FEED
             MECHANISM
AFTERBURNER
 COMBUSTION
     GASES
                     LIQUID OR
                     GASEOUS
                  WASTE INJECTION
 ASH
          FIGURE 3-7   ROTARY KILN INCINERATOR
                              3-42
         Rev.  3
-------
Rotary kiln systems usually have a secondary combustion chamber

or afterburner following the kiln for further combustion of the

volatilized components of solid wastes.




     iii.  Fluidized Bed

     A fluidized bed incinerator consists of a column containing

inert particles such as sand which is referred to as the bed.

Air, driven by a blower, enters the bottom of the bed to fluidize

the sand.  Air passage through the bed promotes rapid and uniform

mixing of the injected waste material within the fluidized bed.

The fluidized bed has an extremely high heat capacity

(approximately three times that of flue gas at the same

temperature), thereby providing a large heat reservoir.  The

injected waste reaches ignition temperature quickly and transfers

the heat of combustion back to the bed.  Continued bed agitation

by the fluidizing air allows larger particles to remain suspended


in the combustion zone.  (See Figure 3-8).




     iv.  Fixed Hearth Incineration

     Fixed hearth incinerators, also called controlled air or

starved air incinerators, are another major technology used for

hazardous waste incineration.  Fixed hearth incineration is a

two-stage combustion process (see Figure 3-9).  Waste is ram-fed
                                         »
into the first stage, or primary chamber, and burned at less than

stoichiometric conditions.   The resultant smoke and pyrolysis


products, consisting primarily of volatile hydrocarbons and
                               3-43                         Rev. 3
-------
WASTE
INJECTION
                      FREEBOARD
                                            GAS TO AIR
                                            POLLUTION
                                            CONTROL
                                               MAKE-UP
                                               SAND
                                              AIR
                          ASH
                       FIGURE 3-8

                 FLUIDIZED BED INCINERATOR
                           3-44
                                                  Rev. 3
-------
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                                 3-45
                                                                           Rev.  3
-------
carbon monoxide, along with the normal products of combustion,

pass to the secondary chamber.  Here,  additional air is injected

to complete the combustion.  This two-stage process generally

yields low stack particulate and carbon monoxide (CO) emissions.

The primary chamber combustion reactions and combustion gas are

maintained at low levels by the starved air conditions so that

particulate entrainment and carryover are minimized.




     v.  Air Pollution Controls

     Following incineration of hazardous wastes, combustion gases

are generally further treated in an air pollution control system.

The presence of chlorine or other halogens in the waste requires

a scrubbing or absorption step to remover HCl and other

halo-acids from the combustion gases.   Ash in the waste is not

destroyed in the combustion process.  Depending on its

composition, ash will either exit as bottom ash, at the discharge

end of a kiln or hearth for example, or as particulate matter

(fly ash) suspended in the combustion gas stream.  Particulate

emissions from most hazardous waste combustion systems generally

have particle diameters less than one micron and require high

efficiency collection devices to minimize air emissions.  In

addition, scrubber systems provide additional buffer against

accidental releases of incompletely destroyed waste products due
                                        V
to poor combustion efficiency or combustion upsets, such as flame

outs.
                               3-46                        Rev. 3
-------
(4)  Waste Characteristics Affecting Performance (WCAP)




     i.  Liquid Injection

     In determining whether liquid injection is likely to achieve

the same level of performance on an untested waste as a

previously tested waste, the Agency will compare dissociation


bond energies of the constituents in the untested and tested


waste.  This parameter is being used as a surrogate indicator of

activation energy which, as discussed previously, destabilizes

molecular bonds.  In theory, the bond dissociation energy would

be equal to the activation energy; however, in practice this is

not always the case.Other energy effects (e.g., vibrational, the

formation of intermediates, and interactions between different


molecular bonds) may have a significant influence on activation

energy.




     Because of the shortcomings of bond energies in estimating

activation energy, EPA analyzed other waste characteristic

parameters to determine if these parameters would provide a

better basis for transferring treatment standards from an

untested waste to a tested waste.  These parameters include heat

of combustion, heat of formation, use of available kinetic data

to predict activation energies, and general structural class.
                                         t>
All of these were rejected for reasons provided below.
                              3-47                         Rev. 3
-------
     The heat of combustion only measures the difference in
energy of the products and reactants; it does not provide
information on the transition state (i.e.,  the energy input
needed to initiate the reaction).  Heat of formation is used as a
predictive tool for whether reactions are likely to proceed;
however, there are a significant number of hazardous constituents
for which these data are not available.  Use of kinetic data were
rejected because these data are limited and could not be used to
calculate free energy values (&G) for the wide range of
hazardous constituents to be addressed by this rule.  Finally,
EPA decided not to use structural classes because the Agency
believes that evaluation of bond dissociation energies allows for
a more direct determination of whether a constituent will be
destabilized.

     ii.  Rotary Kiln/Fluidized Bed/Fixed Hearth
     Unlike liquid injection, these incineration technologies
also generate a residual ash.  Accordingly, in determining
whether these technologies are likely to achieve the same level
of performance on an untested waste as a previously tested waste,
EPA would need to examine the waste characteristics that affect
volatilization of organics from the waste,  as well as,
destruction of the organics, once volatilized.  Relative to
volatilization, EPA will examine thermal conductivity of the
entire waste and boiling point of the various constituents.  As
with liquid injection, EPA will examine bond energies in
                               3-48                         Rev. 3
-------
determining whether treatment standards for scrubber water

residuals can be transferred from a tested waste to an untested

waste.  Below is a discussion of how EPA arrived at thermal

conductivity and boiling point as the best method to assess

volatilization of organics from the waste; the discussion

relative to bond energies is the same for these technologies as

for liquid injection and will not be repeated here.
     Thermal Conductivity

     Consistent with the underlying principles of incineration, a

major factor with regard to whether a particular constituent will

volatilize is the transfer of heat through the waste.  In the

case of rotary kiln, fluidized bed, and fixed hearth

incineration, heat is transferred through the waste by three

mechanisms:  radiation, convection, and conduction.  For a given

incinerator, heat transferred through various wastes by radiation

is more a function of the design and type of incinerator than the

waste being treated.  Accordingly, the type of waste treated will

have a minimal impact on the amount of heat transferred by

radiation.  With regard to convection, EPA also believes that the

type of heat transfer will generally be more a function of the

type and design of incinerator than the waste itself.  However,
                                         *•
EPA is examining particle size as a waste characteristic that may

significantly impact the amount of heat transferred to a waste by

convection and thus impact volatilization of the various organic





                               3-49                         Rev. 3
-------
compounds.  The final type of heat transfer, conduction, is the

one that EPA believes will have the greatest impact on

volatilization of organic constituents.  To measure this

characteristic, EPA will use thermal conductivity; an explanation

of this parameter, as well as, how it can be measured is provided

below.




     Heat flow by conduction is proportional to the temperature

gradient across the material.  The proportionality constant is a

property of the material and referred to as the thermal

conductivity.  (Note:  The analytical method that EPA has

identified for measurement of thermal conductivity is named

"Guarded, Comparative, Longitudinal Heat Flow Technique"; it is

described in Appendix F.)  In theory, thermal conductivity would

always provide a good indication of whether a constituent in an

untested waste would be treated to the same extent in the primary

incinerator chamber as the same constituent in a previously

tested waste.




     In practice, thermal conductivity has some limitations in

assessing the transferability of treatment standards; however,

EPA has not identified a parameter that can provide a better

indication of heat transfer characteristics of a waste.  Below is
                                         V
a discussion of both the limitations associated with thermal

conductivity, as well as other parameters considered.
                               3-50                        Rev. 3
-------
     Thermal conductivity measurements, as part of a treatability

comparison for two different wastes through a single incinerator,

are most meaningful when applied to wastes that are homogeneous

(i.e., major constituents are essentially the same).  As wastes

exhibit greater degrees of non-homogeneity (e.g., significant

concentration of metals in soil), then thermal conductivity

becomes less accurate in predicting treatability because the

measurement essentially reflects heat flow through regions having

the greatest conductivity (i.e., the path of least resistance)

and not heat flow through all parts of the waste.




     BTU value, specific heat, and ash content were also

considered for predicting heat transfer characteristics.  These

parameters can no better account for non-homogeneity than thermal

conductivity; additionally,  they are not directly related to heat

transfer characteristics.  Therefore, these parameters do not

provide a better indication of heat transfer that will occur in

any specific waste.




     Boiling Point

     Once heat is transferred to a constituent within a waste,

then removal of this constituent from the waste will depend on

its volatility.  As a surrogate of volatility, EPA is using
                                         v
boiling point of the constituent.  Compounds with lower boiling

points have higher vapor pressures and, therefore, would be more

likely to vaporize.  The Agency recognizes that this parameter





                               3-51                         Rev. 3
-------
does not take into consideration the impact of other compounds in

the waste on the boiling point of a constituent in a mixture;

however, the Agency is not aware of a better measure of

volatility that can easily be determined.




(5)  Incineration Design and Operating Parameters




     i.  Liquid Injection

     For a liquid injection unit, EPA's analysis of whether the

unit is well designed will focus on (1) the likelihood that

sufficient energy is provided to the waste to overcome the

activation level for breaking molecular bonds and (2) whether

sufficient oxygen is present to convert the waste constituents to

carbon dioxide and water vapor.  The specific design parameters

that the Agency will evaluate to assess whether these conditions

are met are:  temperature, excess oxygen,  and residence time.

Below is a discussion of why EPA believes these parameters to be

important, as well as a discussion of how these parameters will

be monitored during operation.




     It is important to point out that, relative to the

development of land disposed restriction standards, EPA is only


concerned with these design parameters when a quench water or
                                         *•
scrubber water residual is generated from treatment of a


particular waste.  If treatment of a particular waste in a liquid

injection unit would not generate a wastewater stream, then the





                               3-52                         Rev. 3
-------
Agency, for purposes of land disposal treatment standards, would

only be concerned with the waste characteristics that affect

selection of the unit, not the above-mentioned design parameters.




     Temperature

     Temperature is important in that it provides an indirect

measure of the energy available (i.e., BTUs/hr) to overcome the

activation energy of waste constituents.  As the design

temperature increases, the more likely it is that the molecular

bonds will be destabilized and the reaction completed.




     The temperature is normally controlled automatically through

the use of instrumentation which senses the temperature and

automatically adjusts the amount of fuel and/or waste being fed.

The temperature signal transmitted to the controller can be

simultaneously transmitted to a recording device, referred to as

a strip chart, and thereby continuously recorded.  To fully

assess the operation of the unit,  it is important to know not

only the exact location in the incinerator that the temperature

is being monitored but also the location of the design

temperature.




     Excess Oxygen
                                         V
     It is important that the incinerator contain oxygen in

excess of the stiochiometric amount necessary to convert the

organic compounds to carbon dioxide and water vapor.  If
                               3-53                         Rev. 3
-------
insufficient oxygen is present, then destabilized waste

constituents could recombine to the same or other BOAT list

organic compounds and potentially cause the scrubber water to

contain higher concentrations of BOAT list constituents than

would be the case for a well operated unit.




     In practice, the amount of oxygen fed to the incinerator is

controlled by continuous sampling and analysis of the stack gas.

If the amount of oxygen drops below the design value, then the

analyzer transmits a signal to the valve controlling the air

supply and thereby increases the flow of oxygen to the

afterburner.  The analyzer simultaneously transmits a signal to a

recording device so that the amount of excess oxygen can be

continuously recorded.  Again, as with temperature, it is

important to know the location from which the combustion gas is

being sampled.




     Carbon Monoxide

     Carbon monoxide is an important operating parameter because

it provides an indication of the extent to which the waste

organic constituents are being converted to CO_ and water vapor.

As the carbon monoxide level increases, it indicates that greater

amounts of organic waste constituents are unreacted or partially
                                         »•
reacted.  Increased carbon monoxide levels can result from

insufficient excess oxygen, insufficient turbulence in the

combustion zone, or insufficient residence time.
                               3-54                         Rev. 3
-------
     Waste Feed Rate



     The waste feed rate is important to monitor because it is



correlated to the residence time.  The residence time is



associated with a specific BTU energy value of the feed and a



specific volume of combustion gas generated.  Prior to



incineration, the BTU value of the waste is determined through



the use of a laboratory device known as a bomb calorimeter.  The



volume of combustion gas generated from the waste to be



incinerated is determined from an analysis referred to as an



ultimate analysis.  This analysis determines the amount of



elemental constituents present which include carbon, hydrogen,



sulfur, oxygen, nitrogen, and halogens.  Using this analysis plus



the total amount of air added, the volume of combustion gas can



be calculated.  Having determined both the BTU content and the



expected combustion gas volume, the feed rate can be fixed at the



desired residence time.  Continuous monitoring of the feed rate



will determine whether the unit was operated at a rate



corresponding to the designed residence time.







     ii.  Rotary Kiln



     For this incineration, EPA will examine both the primary and



secondary chamber in evaluating the design of a particular



incinerator.  Relative to the primary chamber, EPA's assessment



of design will focus on whether it is likely that sufficient



energy will be provided to the waste in order to volatilize the



waste constituents.  For the secondary chamber,
                               3-55                         Rev. 3
-------
analogous to the sole liquid injection incineration chamber, EPA



will examine the same parameters discussed previously under



liquid injection incineration.  These parameters will not be



discussed again here.







     The particular design parameters to be evaluated for the



primary chamber are:  kiln temperature, residence time, and



revolutions per minute.  Below is a discussion of why EPA



believes these parameters to be important, as well as a



discussion of how these parameters will be monitored during



operation.







     Temperature



     The primary chamber temperature is important, in that it



provides an indirect measure of the energy input  (i.e., BTUs/hr)



that is available for heating the waste.  The higher the



temperature is designed to be in a given kiln, the more likely it



is that the constituents will volatilize.  As discussed earlier



under "Liquid Injection", temperature should be continuously



monitored and recorded.  Additionally, it is important to know



the location of the temperature sensing device in the kiln.








     Residence Time



     This parameter is important in that it affects whether



sufficient heat is transferred to a particular constituent in



order for volatilization to occur.  As the time that the waste is
                               3-56                        Rev. 3
-------
in the kiln is increased, a greater quantity of heat is

transferred to the hazardous waste constituents.  The residence

time will be a function of the specific configuration of the

rotary kiln including the length and diameter of the kiln, the

waste feed rate, and the rate of rotation.




     Revolutions Per Minute (RPM)

     This parameter provides an indication of the turbulence that

occurs in the primary chamber of a rotary kiln.  As the

turbulence increases, the quantity of heat transferred to the

waste would also be expected to increase.  However, as

the RPM value increases, the residence time decreases resulting

in a reduction of the quantity of heat transferred to the waste.

This parameter needs to be carefully evaluated because it

provides a balance between turbulence and residence time.




     iii.  Fluidized Bed

     As discussed previously,  in the section on "Underlying

Principles of Operation", the primary chamber accounts for almost

all of the conversion of organic wastes to carbon dioxide, water

vapor, and acid gas if halogens are present.  The secondary

chamber will generally provide additional residence time for

thermal oxidation of the waste constituents.  Relative to the
                                         V
primary chamber, the parameters that the Agency will examine in

assessing the effectiveness of the design are temperature,

residence time, and bed pressure differential.  The first two





                               3-57                         Rev. 3
-------
were discussed under rotary kiln and will not be discussed here.
The latter, bed pressure differential, is important in that it
provides an indication of the amount of turbulence and,
therefore, indirectly the amount of heat supplied to the waste.
In general, as the pressure drop increases, both the turbulence
and heat supplied increase.  The pressure drop through the bed
should be continuously monitored and recorded to ensure that the
designed valued is achieved.

     iv.  Fixed Hearth
     The design considerations for this incineration unit are
similar to a rotary kiln with the exception that rate of rotation
(i.e., RPMs) is not an applicable design parameter.  For the
primary chamber of this unit, the parameters that the Agency will
examine in assessing how well the unit is designed are the same
as discussed under rotary kiln; for the secondary chamber (i.e.,
afterburner), the design and operating parameters of concern are
the same as previously discussed under "Liquid Injection".
                               3-58                        Rev. 3
-------
3.3  Performance Data for Wastewaters

     Of the three demonstrated treatment technology systems
defined in Section 3.2, the Agency collected performance data for
the system consisting of liquid/liquid extraction followed by
steam stripping and activated carbon adsorption.  This treatment
system was chosen by the EPA for collecting performance data
because the liquid/liquid extraction step in this three-step
treatment process provides an incremental reduction in the level
of organics over that obtained by either of the other two
treatment processes.

     Performance data collected by EPA for liquid/liquid
extraction followed by stream stripping and carbon adsorption are
presented in Tables 3-1 to 3-5.  Tables 3-1 through 3-5 present
the analytical data for sample sets 1 through 5 collected during
the Agency's sampling visit.  The untreated K103 and K104 wastes
and the combined treated steam leaving the carbon adsorption beds
for each sample set were analyzed for BOAT volatile and
semivolatile organic compounds, metals, inorganic compounds, and
other parameters.

     Included in Tables 3-1 through 3-5 are the design values and
actual operating ranges for the key operating parameters of the
aniline liquid/liquid extractor, nitrobenzene liquid/liquid
                               3-59                         Rev. 3
-------
TABLE  3-1   TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION  FOLLOWED BY STEAM STRIPPING AND
           ACTIVATED CARBON ADSORPTION - EPA COLLECTED  DATA8
                                          SAMPLE SET  1
BDAT CONSTITUENTS DETECTED
Volatile Organic Compounds
4 Benzene
48 Trichloromonof luoromethane
Semivolatile Organic Compounds
56 Aniline
101 2,4-Dinitrophenol
126 Nitrobenzene
142 Phenol
Metals
155 Arsenic
156 Barium
159 Chromium
160 Copper
161 Lead
163 Nickel
167 Vanadium
168 Zinc
Inorganics
169 Total Cyanides
170 Fluorides
171 Sulfides
UNTREATED
K103
-------
TABLE 3-1  (Continued)  TREATMENT  DATA FOR  LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM
           STRIPPING AND ACTIVATED  CARBON  ADSORPTION  - EPA COLLECTED DATA3
                                            SAMPLE SET 1
OPERATING PARAMETERS
      Design Value
Operating Range
Aniline Liquid/Liquid Extractor :

Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor (°C)
      7,000 - 25,000
          9 - 10**

          40.0**
14,400 - 14,500
      10.3

      13.0
Nitrobenzene Liquid/Liquid Extractor
Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
                o
     Extractor ( C)
     27,000 - 35,000
         Max. 2.4

        25.0 - 65.0
21,300 - 46,000
       0.2

      39.0
Steam Stripper :

                        o
Top Column Temperature ( C)
Pressure Drop Across the
     ColumnCinches of water)
Feed Rate to Steam StripperCIbs/hr)
         Min. 95.0

         Max. 90.0
Min. 20,000,  Max.  90,000
      95***

 44.26 - 51.00
59,400 - 59,480
Activated Carbon Adsorption:

Feed Rate to the System (Ibs/hr)
Feed pH to the System
Feed Temperature to the
             o
     System ( C)
Total Organic Carbon in treated
     waste (mg/l)
Calculated Residence time (minutes)
         Max. 65,300
         Min. 7.0

            40.0**
         Max. 250
         Instantaneous
         Min. 85
61,600 - 68,600
      10.6

      25.0
      79.3

    81 - 90
  a - Onsite Engineering Report  for  E.  I.  duPont de Nemours, Inc., Beaumont, Texas,
      Tables 4-1 through 4-3,  6-6, 6-8,  and 6-14.
 ** - Not controlled.   Normal  operating  value  is given.
*** - Mid column substituted for top column temperature due to technical difficulties.
                                                    3-61
                                                       Rev.   3
-------
TABLE 3-2   TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED  BY STEAM STRIPPING AND
           ACTIVATED CARBON ADSORPTION  - EPA COLLECTED DATA8
                                          SAMPLE SET 2
BOAT CONSTITUENTS DETECTED
Volatile Organic Compounds
4 Benzene
48 Trichloromonof luoromethane
Semi volatile Organic Compounds
56 Aniline
101 2,4-Dinitrophenol
126 Nitrobenzene
142 Phenol
Metals
155 Arsenic
156 Barium
159 Chromium
160 Copper
161 Lead
163 Nickel
167 Vanadium
168 Zinc
Inorganics
169 Total Cyanides
170 Fluorides
171 Sulfides
UNTREATED
K103
(mg/l)

73
<5

33.000
<7,500
<1,500
<1,500

<0.010
<0.001
<0.007
<0.006
<0.005
<0.011
<0.006
0.003

0.0595
<0.20
89.0
WASTE
K104

320
<20

<150
<750
2,200
<150

<0.100
0.0015
0.097
<0.006
<0.100
0.055
<0.006
0.011

3.30
<0.20
<1.0*
TREATED WASTE
(mg/l)

<0.005
0.010

<0.030
0.320
<0.030
<0.030

<0.100
0.042
0.024
<0.006
<0.050
<0.011
0.012
0.052

0.597
0.420
<1.0*
  * - Negative Interference Value
                                                                                           Cont i nued
                                                   3-62
                                                                                                 Rev.  3
-------
TABLE 3-2  (Continued)  TREATMENT  DATA  FOR  LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM
           STRIPPING AND  ACTIVATED  CARBON  ADSORPTION - EPA COLLECTED DATA3
                                           SAMPLE SET 2
OPERATING PARAMETERS
      Design Value
Operating Range
Aniline Liquid/Liquid Extractor :

Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor (°C)
      7,000 - 25.000
          9 - 10**

          40.0**
15,900 - 16,000
      10.3

      22.0
Nitrobenzene Liquid/Liquid Extractor :
Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor (°C)
     27,000 - 35,000
         Max. 2.4

        25.0 - 65.0
 9,800 - 26,000
      0.2

      43.0
Steam Stripper :
                        o
Top Column Temperature ( C)
Pressure Drop Across the
     ColunrKinches of water)
Feed Rate to Steam Stripper(Ibs/hr)
         Min. 95.0

         Max. 90.0
Min. 20,000, Max.  90,000
  102.2 - 103.3

 42.40 - 58.00
49,000 - 60,100
Activated Carbon Adsorption:
Feed Rate to the System (Ibs/hr)
Feed pH to the System
Feed Temperature to the
o
System ( C)
Total Organic Carbon in treated
waste (ing/ 1)
Calculated Residence time (minutes)
Max. 65,300
Min. 7.0


40.0**
Max. 250
Instantaneous
Min. 85
63,000 - 76,
4.6


28.0

73.5
73 - 88
000







  a - Onsite Engineering  Report  for  E.  I. duPont de Nemours, Inc., Beaumont, Texas,
      Tables 4-1  through  4-3,  6-6, 6-8,  and 6-14.
 ** - Not controlled.   Normal  operating  value  is given.
                                                    3-63
                                                       Rev.  3
-------
TABLE 3-3   TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED  BY  STEAM STRIPPING AND
           ACTIVATED CARBON ADSORPTION  - EPA COLLECTED DATA8
                                          SAMPLE SET 3
BOAT CONSTITUENTS DETECTED
Volatile Organic Compounds
4 Benzene
48 Trichlorof luoromethane
Semi volatile Organic Compounds
56 Aniline
101 2,4-Dinitrophenol
126 Nitrobenzene
142 Phenol
Metals
155 Arsenic
156 Barium
159 Chromium
160 Copper
161 Lead
163 Nickel
167 Vanadium
168 Zinc
Inorganics
169 Total Cyanides
170 Fluorides
171 Sulfides
UNTREATED
K103
(ntg/l)

65
<2.5

39,000
<15,000
<3,000
<3,000

<0.010
<0.001
<0.007
<0.006
<0.005
<0.011
<0.006
0.0099

0.0411
<0.20
74.0
WASTE
K104

70
<5

<150
<750
2,300
<150

<0.010
0.011
<0.007
0.0075
<0.005
<0.011
O.006
0.031

5.70
<0.20
<1.0*
TREATED WASTE
(mg/l>

0.018
<0.005

4.20
<0.760
<0.150
<0.150

<0.010
0.068
0.008
<0.006
<0.005
<0.011
0.0091
0.016

0.201
0.220
<1.0*
  * - Negative Interference Value
                                                                                           Cont i nued
                                                   3-64
Rev.  3
-------
TABLE 3-3  (Continued) TREATMENT  DATA FOR  LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM
           STRIPPING AND  ACTIVATED  CARBON  ADSORPTION  - EPA COLLECTED DATA9
                                            SAMPLE SET 3
OPERATING PARAMETERS
      Design Value
Operating Range
Aniline Liquid/Liquid Extractor :

Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor (°C)
      7,000 - 25,000
          9 - 10**

          10.0**
17,600 - 17,800
      10.1

     24.0
Nitrobenzene Liquid/Liquid Extractor
Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
                o
     Extractor ( C)
     27,000 - 35,000
         Max. 2.4

        25.0 - 65.0
24,100 - 33,000
       5.7

      42.5
Steam Stripper :
                        o
Top Column Temperature ( C)
Pressure Drop Across the
     Column(inches of water)
Feed Rate to Steam Stripper(Ibs/hr)

Activated Carbon Adsorption:

Feed Rate to the System (Ibs/hr)
Feed pH to the System
Feed Temperature to the
             o
     System ( C)
Total Organic Carbon in treated
     waste (mg/l)
Calculated Residence time (minutes)
         Min. 95.0

         Max. 90.0
Min. 20,000, Max. 90,000
         Max. 65,300
         Min. 7.0

            40.0**
         Max. 250
         Instantaneous
         Min. 85
 102.6 - 103.0

 46.42 - 50.33
60,200 - 60,400
57,700 - 58,140
      3.1

     44.0
      10.8

    96 - 97
  a - Onsite Engineering Report  for  E.  I. duPont de Nemours, Inc., Beaumont, Texas,
      Tables 4-1  through 4-3,  6-6, 6-8,  and 6-14.
 ** - Not controlled.   Normal  operating  value  is given.
                                                    3-65
                                                       Rev.   3
-------
TABLE 3-4  TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION  FOLLOWED BY STEAM STRIPPING AND
          ACTIVATED CARBON ADSORPTION - EPA COLLECTED  DATA8
                                          SAMPLE SET 4
BOAT CONSTITUENTS DETECTED
Volatile Organic Compounds
4 Benzene
48 Trichlorof luoromethane
Semi volatile Organic Compounds
56 Aniline
101 2,4-Dinitrophenol
126 Nitrobenzene
142 Phenol
Metals
155 Arsenic
156 Barium
159 Chromium
160 Copper
161 Lead
163 Nickel
167 Vanadium
168 Zinc
Inorganics
169 Total Cyanides
170 Fluorides
171 Sulfides
UNTREATED
K103
(mg/D

55
<2.5

39,000
<15,000
<3.000
<3,000

0.021
<0.001
<0.007
<0.006
<0.005
<0.011
<0.006
0.018

<0.0100
<0.20
62.0
WASTE
K104

11
<0.5

<300
<1,500
2,900
<300

<0.010
0.017
<0.007
<0.006
<0.005
<0.011
<0.006
0.064

3.06
<0.20
<1.0*
TREATED WASTE
Ong/t)

0.019
<0.005

<0.030
0.260
<0.030
<0.030

<0.500
0.076
<0.007
<0.006
<0.005
0.015
<0.006
0.033

0.156
0.220
<1.0*
  * - Negative Interference Value
                                                                                          Cont i nued
                                                  3-66
Rev.  3
-------
TABLE 3-4  (Continued)  TREATMENT  DATA  FOR  LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM
           STRIPPING AND ACTIVATED  CARBON  ADSORPTION - EPA COLLECTED DATA
                                            SAMPLE SET 4
OPERATING PARAMETERS
      Design Value
Operating Range
Aniline Liquid/Liquid Extractor  :

Feed Rate to the Extractor 
-------
TABLE 3-5   TREATMENT DATA FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM STRIPPING AND
           ACTIVATED CARBON ADSORPTION  - EPA COLLECTED DATA8
                                          SAMPLE SET 5
BOAT CONSTITUENTS DETECTED
Volatile Organic Compounds
4 Benzene
48 Trichlorof luoromethane
Semi volatile Organic Compounds
56 Aniline
101 2,4-Dinitrophenol
126 Nitrobenzene
142 Phenol
Metals
155 Arsenic
156 Barium
159 Chromium
160 Copper
161 Lead
163 Nickel
167 Vanadium
168 Zinc
Inorganics
169 Total Cyanides
170 Fluorides
171 Sulfides
UNTREATED WASTE
K103 K104
(mg/l)

32
<2.5

53,000
<15,000
<3,000
<3,000

<0.500
<0.001
<0.007
<0.006
0.006
<0.011
<0.006
0.014

0.0384
<0.20
80.0

4.5
<0.25

<300
<1,500
3,900
<300

<0.500
0.013
0.0071
<0.006
<0.050
0.014
<0.006
0.014

4.44
<0.20
<1.0*
TREATED WASTE
(mg/l)

0.011
<0.005

0.960
0.230
<0.030
0.150

<0.010
0.073
0.017
<0.006
<0.100
0.030
<0.006
0.012

0.129
0.620
<1.0*
      Negative Interference Value
                                                                                           Cont i nued
                                                   3-68
Rev.  3
-------
TABLE 3-5  (Continued)  TREATMENT DATA  FOR LIQUID/LIQUID EXTRACTION FOLLOWED BY STEAM
           STRIPPING AND  ACTIVATED  CARBON ADSORPTION - EPA COLLECTED DATA8
                                            SAMPLE SET 5
OPERATING PARAMETERS
      Design Value
Operating Range
Aniline Liquid/Liquid Extractor  :

Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor ( C)
      7,000 - 25,000
          9 - 10**

          40.0**
14.800 - 14,900
      10.2

      28.0
Nitrobenzene Liquid/Liquid Extractor
Feed Rate to the Extractor (Ibs/hr)
Feed pH to the Extractor
Feed Temperature to the
     Extractor < C)
     27,000 - 35,000
         Max. 2.4

        25.0 - 65.0
24,700 - 31,500
       1.5

      47.5
Steam Stripper :

                        o
Top Column Temperature ( C)
Pressure Drop Across the
     Column(inches of water)
Feed Rate to Steam Stripper(Ibs/hr)
         Min. 95.0

         Max. 90.0
Min. 20,000, Max.  90,000
  102.6 - 102.7

 44.80 - 51.80
57,590 - 57,660
Activated Carbon Adsorption:
Feed Rate to the System (Ibs/hr)
Feed pH to the System
Feed Temperature to the
0
System ( C)
Total Organic Carbon in treated
waste (mg/l)
Calculated Residence time (minutes)
Max. 65,300
Min. 7.0


40.0**
Max. 250
Instantaneous
Min. 85
52,200 - 61,500
3.5


33.5
7.0

91 - 107
  a - Onsite Engineering Report  for E.  I. duPont de Nemours, Inc., Beaumont, Texas,
      Tables 4-1  through 4-3,  6-6, 6-8, and 6-14.
 ** - Not controlled.   Normal  operating value is given.
                                                    3-69
                                                                                                   Rev.  3
-------
extractor, steam stripper, and activated carbon adsorption beds



for each sample set collected.







3.4  Other Applicable Treatment Technologies







     The Agency does not believe that other technologies are



applicable for treatment of K103 and K104 wastewaters because of



various physical and chemical characteristics of the wastewaters.



For a detailed description of the physical and chemical



characteristics affecting treatment selection, see BOAT



Background Document for the First Third Wastes,  Volume 1,



Section 2.







     Liquid/liquid extraction followed by steam stripping and



activated carbon adsorption is judged to be available to treat



K103 and K104 wastewaters, and incineration is judged to be



available to treat K103 and K104 nonwastewaters.  The Agency



believes these technologies to be available because (1) the



Agency does not have information showing that this technology



poses a greater total risk to human health and the environment



that land disposal; (2) this technology is commercially



available; and (3) this technology provides a substantial



reduction  in the levels of BOAT constituents present in waste



K103 and K104.
                               3-70                        Rev. 3
-------
4.  IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TREATMENT
                   TECHNOLOGY FOR K103  AND K104
4.1  Introduction




     The previous section described applicable treatment

technologies for waste codes K103 and K104, and the available

performance data for these technologies.  This section describes

how the performance data collected by the Agency was evaluated to

determine which treatment technology system should be considered

BOAT for waste codes K103 and K104.  Several treatment trains are

considered in this section as BOAT for wastewaters.  They consist

of:

     o    liquid/liquid extraction,

     o    liquid/liquid extraction followed by steam stripping,

     o    liquid/liquid extraction followed by steam stripping

          and activated carbon adsorption.




     The use of activated carbon adsorption for treatment of K103

and K104 wastewaters generates a nonwastewater, spent carbon.

The treatment considered in this section as BOAT for the

nonwastewaters is rotary kiln incineration.




     The topics covered in this section include descriptions of
                                         V
the data screening process employed for selecting BOAT, the

methods used to ensure accuracy of the analytical data, and the
                               4-1                         Rev. 3
-------
analysis of variance (ANOVA) tests performed in identifying the

best technology for the treatment of K103 and K104 wastes.



     As discussed in Section 3, the Agency collected performance

data for the treatment of waste codes K103 and K104 from one

treatment technology system:  liquid/liquid extraction followed

by steam stripping and activated carbon adsorption.  No

additional performance data were available for the treatment of

K103 and K104 wastes.  However, the Agency is using and comparing

data taken from various components of the treatment train to

determine BDAT.  Performance data were not available for the

treatment of K103 and K104 nonwastewaters.



     In general, performance data are screened according to the

following three conditions:

     o    proper design and operation of the treatment system;

     o    the existence of quality assurance/quality control
          measures in the data analysis; and

     o    the use of proper analytical tests in assessing
          treatment performance.

Sets of performance data which do not meet these three conditions

are not considered in the selection of BDAT.  In addition, if

performance data indicate that the treatment system was not well-

designed and well-operated at the time of testing, these data

would also not be used.
                               4-2                         Rev. 3
-------
     The remaining performance data are then corrected to account

for incomplete recovery of certain constituents during the

analyses.  Finally, in cases where the Agency has adequate

performance data for treatment of the waste by more than one

technology, an analysis of variance (ANOVA) test is used to

select the best treatment technology.



4.2  Data Screening



     In the selection of BOAT for treatment of K103 and K104

wastewaters, the only performance data available were those

collected during the Agency's sampling visit.  Five data sets

were collected by the Agency for treatment of the wastewaters by

liquid/liquid extraction followed by steam stripping and carbon

adsorption.  These data were evaluated to determine whether any

of the data represented poor design or operation of the system.

One of the data sets (Sample Set #3) was deleted due to poor

operation of the carbon adsorption unit during the time data were

being collected.  This was indicated by a higher than normal

system temperature and a relatively high aniline concentration in

the treated waste.  The four remaining data sets were used for

the development of treatment standards for K103 and K104

wastewaters.  These data sets are sample sets 1, 2, 4 and 5.
                                         k-


     Toxic Characteristic Leaching Procedure (TCLP) data were not

used in setting treatment standards for waste codes K103 and K104
                               4-3                         Rev. 3
-------
because metals were not identified as one of the classes of BOAT

list constituents for regulation (see Section 5 for further

details).   For a discussion on the use of TCLP data in setting

treatment standards, refer to Section 1 of this background

document.




     In instances where a selected constituent was not detected

in the treated waste, the treated value for that constituent was

assumed to be the practical quantification level.  This was the

case for the following constituents:  (1) benzene in Sample Set

#2; (2) aniline in Sample Sets #1, #2, and #4; (3) nitrobenzene

in Sample Sets #1, #2, #4, and #5; (4) phenol in Sample Sets #1,

#2, and #4.  Analytical values for the treated waste are

presented in Table 4-1.




4.3.  Data Accuracy




     After data were eliminated from consideration for analysis

of BOAT based on the screening tests, the Agency adjusted the

remaining data using analytical recovery values in order to take

into account analytical interferences and incomplete recoveries

associated with the chemical makeup of the sample.  The Agency

developed the recovery data  (also referred to as accuracy data),
                                         »-
by first analyzing a waste for a given constituent and then by

adding a known amount of the same constituent  (i.e., spike) to


the waste material.  The total amount recovered after spiking,
                               4-4                         Rev.  3
-------
TABLE 4-1   Treatment Data Used for Regulation of K103 and K104 Wastewaters
                                 ANALYTICAL CONCENTRATIONS  (1)
BOAT List
Constituent
Benzene
Ani line
2,4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides
Sample Set 1
(total)
(mg/l)
0.042
<0.030
0.380
<0.030
<0.030
0.565
Sample Set 2
(total)
(mg/l)
<0.005
<0.030
0.320
<0.030
<0.030
0.597
Sample Set 4
(total)
(mg/l)
0.019
<0.030
0.260
<0.030
<0.030
0.156
Sample Set 5
(total)
(mg/l)
0.011
0.960
0.230
<0.030
0.150
0.129
ACCURACY-CORRECTED CONCENTRATIONS (2)
BOAT List
Const i tuent
Benzene
Ani line
2,4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides
Sample Set 1
(total)
(mg/l)
0.055
0.033
0.475
0.026
0.143
0.785
Sample Set 2
(total)
(mg/l)
0.007
0.033
0.400
0.026
0.143
0.830
Sample Set 4
(total)
(mg/l)
0.025
0.033
0.325
0.026
0.143
0.217
Sample Set 5
(total)
(mg/l)
0.015
1.056
0.288
0.026
0.714
0.179
   1.  Onsite Engineering Report for E.I. du Pont de Nemours,  Inc.,  Beaumont,
       Texas, Tables 6-14.

   2.  Calculations shown in Appendix D of this Background Document.

                                                4-5
Rev.  3
-------
minus the initial concentration in the sample, divided by the



amount added, is the recovery value.  At least two recovery



values were calculated for spiked constituents, and the



analytical data were adjusted for accuracy using the lowest



recovery value for each constituent.







     This was accomplished by calculating an accuracy factor from



the percent recoveries for each selected constituent.  The



reciprocal of the lower of the two recovery values divided by



100, yields the accuracy factor.  The corrected concentration for



each sample set is obtained by multiplying the accuracy factor by



the raw data value.  The actual recovery values and accuracy



factors for the selected constituents are presented in



Appendix E.








     The accuracy factors calculated for the selected



constituents varied from a high value of 4.76 for phenol to a low



value of 0.87 for nitrobenzene.  The corrected concentration



values for the selected constituents are shown for the four data



sets in Table 6-1.  These corrected concentrations values were



obtained by multiplying the accuracy factors  (Appendix E) by the



concentration values for the selected constituents in the treated



waste.  An arithmetic average value, representing the treated



waste concentration, was calculated for each selected constituent



from the four corrected values.  These averages are presented in



Table 6-1.  These adjusted values for the treatment technology
                               4-6                         Rev. 3
-------
system consisting of liquid/liquid extraction followed by steam

stripping and activated carbon adsorption were then used to

determine BDAT for waste codes K103 and K104.



4.4  Analysis of Variance



     In cases where the Agency has adequate performance data on

treatment of the same or similar wastes using more than one

technology, an analysis of variance (ANOVA) test is performed to

determine if one of the technologies provides significantly the

best treatment than the others.  In cases where a particular

treatment technology is shown to provide better treatment, the

treatment standards will be used on this best technology.  The

procedure followed for the analysis of variance (ANOVA) test is

described in  Appendix A.



     In order to determine BDAT for waste codes K103 and K104,

three combinations of demonstrated technologies, for which

adequate performance data were available, were considered for the

treatment of these wastes:

     o    Liquid/liquid extraction,

     o    Liquid/liquid extraction followed by steam stripping,
          and

     o    Liquid/liquid extraction followed by steam stripping
          and activated carbon adsorption.
                               4-7                         Rev. 3
-------
     The corrected data for sample sets 1, 2, 4, and 5 were used

to perform analysis of variance (ANOVA) tests to compare these

three technology combinations.  The three combinations of

treatment technologies were compared based on the concentration

of primary waste constituents (benzene, aniline, nitrobenzene,

phenol, 2,4-dinitrophenol, and total cyanides) in the treated

waste.  The rationale for selecting these constituents for the

ANOVA comparison is presented in Section 6.




     The statistical results of the ANOVA test for liquid/liquid

extraction followed by steam stripping versus liquid/liquid

extraction indicate the following:




     1)   Liquid/liquid extraction followed by steam stripping

          provides significantly better treatment for benzene and

          nitrobenzene in waste codes K103 and K104 than

          liquid/liquid extraction alone.




     2)   Liquid/liquid extraction followed by steam stripping

          provides equivalent treatment for total cyanides in

          waste codes K103 and K104 compared to liquid/liquid

          extraction alone.



                                         »•
     3)   Insufficient data exist to compare the treatment for

          phenol, aniline, and 2,4-dinitrophenol achieved by
                               4-8                         Rev. 3
-------
          liquid/liquid extraction alone with that achieved by



          liquid/liquid extraction followed by steam stripping.







     The statistical results of the ANOVA test of liquid/liquid



extraction followed by steam stripping and activated carbon



adsorption versus liquid/liquid extraction followed by steam



stripping indicate the following:







     1)    Liquid/liquid extraction followed by steam stripping



          and activated carbon adsorption provides significantly



          better treatment for aniline,  2,4-dinitrophenol, phenol



          and total cyanides in waste codes K103 and K104 than



          liquid/liquid extraction followed by steam stripping.







     2)    Liquid/liquid extraction followed by steam stripping



          and activated carbon adsorption provides equivalent



          treatment for benzene in waste codes K103 and K104



          compared to liquid/liquid extraction followed by steam



          stripping.







     3)    Insufficient data exist to compare the treatment for



          nitrobenzene achieved by liquid/liquid extraction



          followed by steam stripping with that achieved by



          liquid/liquid extraction followed by steam stripping



          and activated carbon adsorption.
                               4-9                         Rev. 3
-------
     The three-step treatment technology system consisting of



liquid/liquid extraction followed by steam stripping and



activated carbon adsorption provides significantly better or



equivalent treatment overall for the primary constituents present



in waste codes K103 and K104 when compared either liquid/liquid



extraction alone or liquid/liquid extraction followed by steam



stripping.  Therefore, the Agency has chosen this three-step



treatment system to be BOAT for waste codes K103 and K104.
                               4-10                         Rev. 3
-------
              5.  SELECTION OF  REGULATED CONSTITUENTS
     In the previous section, the best demonstrated available



technology (BOAT) for treating the wastewater forms of waste



codes K103 and K104 was determined to be liquid/liquid extraction



followed by steam stripping and activated carbon adsorption.







     The two nonwastewater forms of K103 and K104 are as follows:



spent carbon from the activated carbon adsorber and the solvent-



extract stream from the nitrobenzene liquid/liquid extractor.



Based on analysis of the influent and effluent streams (see



Tables 6-13 and 6-14 in the OER for K103 and K104) from the



activated carbon adsorber, the Agency expects the spent carbon to



contain the following constituents:  benzene, aniline, 2,4-



dinitrophenol, nitrobenzene, phenol, and cyanides.  Rotary kiln



incineration has been demonstrated on wastes that are similar to



the spent carbon from the activated carbon adsorber.  Therefore,



the Agency believes that rotary kiln incineration is BOAT for the



spent carbon from the activated carbon adsorber.







     Rotary kiln incineration has also been demonstrated on



wastes that are similar to the solvent-extract stream from the



nitrobenzene liquid/liquid extractor.  Therefore, the Agency



believes that rotary kiln incineration is BOAT for the solvent-



extract from the nitrobenzene liquid/liquid extractor.  In this



section, the necessary constituents are identified for assuring







                               5-1                         Rev. 3
-------
the most effective treatment of the wastes.  This is done by

following a three-step procedure:



     o    identifying the BOAT list constituents found in both
          the untreated and treated waste;

     o    determining the classes of BDAT list constituents
          present, and

     o    selecting the regulated constituents.


     As discussed in Section 1, the Agency has developed a list

of hazardous constituents (Table 1-1) from which the constituents

to be regulated are selected.  The list is a "growing list" that

does not preclude the addition of new constituents as additional

key parameters are identified.  The list is divided into the

following categories:  volatile organics, semivolatile organics,

metals, inorganics, organochlorine pesticides, phenoxyacetic acid

herbicides, organophosphorous pesticides, PCBs, and dioxins and

furans.  The constituents in each category have similar chemical

properties and are expected to behave similarly during treatment,

with the exception of the inorganics.


5.1  Identification of BDAT List Constituents in the Untreated
     and Treated Waste


     Using EPA-collected data, the Agency identified those

constituents that were detected in the untreated and treated
                                         V
waste.  The BDAT list of constituents (see Table 1-1, Section

1.0) provided the target list of constituents.  EPA collected

five sets of data at one facility (see the Onsite Engineering
                               5-2                         Rev. 3
-------
Report for K103 and K104 for more details) to evaluate the

treatment of the wastewater forms of waste codes K103 and K104 by

liquid/liquid extraction followed by steam stripping and

activated carbon adsorption.  One of the five data sets (data set

#3) was eliminated because the activated carbon adsorber was not

well-operated during the sampling interval.  Poor operation of

the activated carbon adsorption system was indicated by a higher

than normal system temperature and a relatively high aniline

concentration in the treated waste.  The remaining four data sets

were used to identify the constituents detected in the untreated

and treated waste.  The detection limits for the BOAT list of

constituents are presented in Appendix C.




     Table 5-1 presents the BOAT list as discussed in Section 1.

It indicates which of the BOAT list constituents were analyzed in

the untreated and treated waste.  This table also gives the

concentrations of those BOAT list constituents which were

detected.  As shown in Table 5-1, the following constituents were

detected in the untreated waste K103: benzene, aniline, arsenic,

lead, zinc, total cyanides, and sulfides.  The following

constituents were detected in the untreated waste K104: benzene,

nitrobenzene, barium, chromium, copper, nickel, zinc, total

cyanides, and sulfides.  The following constituents were detected
                                        V
in the treated waste (K103 and K104): benzene, aniline,

2,4-dinitrophenol, trichloromonofluoromethane, phenol, barium,

chromium, nickel, vanadium, zinc, total cyanides, and fluorides.
                               5-3                         Rev. 3
-------
TABLE  5-1  BOAT List  Constituents in Untreated and Treated Waste
Parameter
Untreated
K103
(mg/l)
Untreated
K104
(mg/l)
Treated
K103/K104
(mg/l)
Volatiles
222
1
2
3
4
5
6
223
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
224
225
226
30
227
31
214
32
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
Carbon Tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-1,3-butadiene
Ch 1 orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1,2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Di bromomethane
trans- 1,4-Dichloro-2-butene
D i ch 1 orodi f I uoromethane
1, 1-Dichloroethene
1,2-Di Chloroethane
1, 1-Dichloroethylene
trans- 1,2-Dichloroethene
1 , 2 - D i ch I oropropane
trans- 1 ,3-D ich loropropene
cis-1,3-Dichloropropene
1,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
ND
ND
ND
NO
32 - 81
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.5 - 320
ND
ND
ND
ND
ND
NO
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.011 - 0.042
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
 ND - Not detected
Continued
                                             5-4
                                                                                         Rev.  3
-------
TABLE 5-1   BOAT  List Constituents in Untreated and Treated Waste (Continued)
Untreated Untreated
Parameter K103 K104
(mg/1) (mg/O
Treated
K103/K104
(mg/l)
Volatiles (continued)
33
228
34
229
35
37
38
230
39
40
41
42
43
44
45
46
47
48
49
231
50
215
216
217
Isobutyl alcohol
Hethanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methylacryloni tri le
Methylene chloride
2-Nitropropane
Pyridine
1, 1,1,2-Tetrachloroethane
1,1.2,2-Tetrachloroethane
Tetrachloroethene
Toluene
T r i bromomethane
1,1, 1 -Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichloromonof lurexnethane
1 ,2,3-Trichloropropane
1, 1,2-Trichloro- 1,2,2- tri fluoroethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
NO
ND
NO
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.007 - 0.010
ND
ND
ND
ND
ND
NO
Semivolatiles
51
52
53
54
55
56
57
58
59
218
60
61
62
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Aniline 33000
Anthracene
Arami te
Benz ( a ) anth racene
Benzal chloride
Benzenethiol
Benz i dine
Benzo(a)pyrene
ND
ND
ND
ND
ND
- 53000
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.96**
ND
ND
ND
ND
ND
ND
ND
ND - Not detected
** - Indicates that only one sample contained this constituent at detectable levels.

                                               5-5
Continued

 Rev.  3
-------
TABLE  5-1  BOAT List Constituents in Untreated and Treated Waste (Continued)
Parameter
Untreated
K103
(mg/l)
Untreated
K104
(mg/l)
Treated
K103/K104
(mg/l)
Semivolatiles (continued)
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
232
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
BenzoC b) f I uoranthene
Benzo(ghi )perylene
Benzo( k ) f I uoranthene
p-Benzoquinone
Bis(2-chloroethoxy)ethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropy)ether
Bis(2-ethylhexy)phthalate
4-Bromophenyl phenyt ether
Butyl benzyl phthlate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroaniline
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitrile
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Dibenz(a,h)anthracene
D i benzo(a, e)pyrene
Dibenzo(a,i)pyrene
m- D i ch I orobenzene
o-Dichlorobenzene
p-D i ch I orobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Di ethyl phthalate
3,3'-Dimethyoxlbenzidine
p-Dimethylaminoazobenzene
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dini trobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.23 - 0.38
 ND -  Not detected
                                              5-6
Rev.  3
-------
TABLE 5-1  BOAT List Constituents in Untreated and Treated Waste  (Continued)
Parameter
Untreated
K103
(mg/l)
Untreated
K104
(mg/l)
Treated
K103/K104
(mg/l)
Semivolatiles (cont.)
102
103
104
105
106
219
107
108
109
110
111
112
113
114
115
116
117
118
119
120
36
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
Diphenylni trosamine
1,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexach lorobenzene
Hexachlorobutadiene
Hexach I orocyc I opentadi ene
Hexach loroethane
Hexach loroph ene
Hexach I oropropene
Indeno(1,2,3-cd)pyrene
Isosafrole
Methapyrilene
3-Hethycholanthrene
4,4'-Hethylenebis(2-chloroani line)
Methyl methanesulfonate
Napthalene
1,4-Naphthoquinone
1-Napthylamine
2-Napthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Ni trosodiethylamine
N-Nitrosodimethylamine
N -N i trosomethy I ethy 1 ami ne
N-Nitrosomorpholine
N-Nitrosopiperidine
n-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pentach I orobenzene
Pentach loroethane
Pentach I oron i t robenzene
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2200 - 3900
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND -  Not detected
                                              5-7
Rev.  3
-------
TABLE 5-1   BOAT List Constituents  in Untreated and Treated Waste (Continued)
Parameter
Semivolatiles (cont.)
139 Pentachlorophenol
140 Phenacetin
141 Phenanthrene
142 Phenol
220 Phthalic anhydride
143 2-Picoline
144 Pronamide
145 Pyrene
146 Resorcinol
147 Safrole
148 1,2,4,5-Tetrachlorobenzene
149 2,3,4, 6-Tetrachlorophenol
150 1,2,4-Trichlorobenzene
151 2,4,5-Trichlorophenol
152 2,4.6-Trichlorophenol
153 Tris(2,3-dibromopropyl)phosphate
Hetals
154 Antimony
155 Arsenic
156 Barium
157 Beryllium
158 Cadmium
159 Chromium
221 Chromium (hexavalent)
160 Copper
161 Lead
162 Mercury
163 Nickel
164 Selenium
165 Si Iver
166 Thallium
167 Vanadium
168 Zinc
Inorganics
169 Cyanide
170 Fluoride
171 Sulfide
Untreated
£103
(mg/l)

NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND
0.021**
ND
ND
ND
ND
ND
ND
0.006**
ND
ND
ND
ND
ND
ND
0.003 - 0.021

0.038 - 0.075
ND
62.0 - 89.0
Untreated
K104
(mg/l)

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
0.0015 - 0.017
ND
ND
0.007 - 0.432
ND
0.012**
ND
ND
0.014 - 0.238
ND
ND
ND
ND
0.011 - 0.079

3.06 - 6.28
ND
ND
Treated
K103/K104
(mg/l)

ND
ND
ND
0.15**
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
0.032 - 0.076
ND
ND
0.0097 - 0.024
ND
ND
ND
ND
0.015 - 0.030
ND
ND
ND
0.012 - 0.014
0.012 - 0.058

0.129 - 0.597
0.220 - 0.620
ND
**  - Indicates that only one sample contained this constituent at detectable levels.




                                               5-8
Continued




 Rev.  3
-------
TABLE 5-1  BOAT List Constituents in Untreated and Treated Waste (Continued)
Parameter
Organochlorine Pesticides
172 Aldrin
173 alpha-BHC
174 beta-BHC
175 delta- BHC
176 gamma -BHC
177 Chlordane
178 ODD
179 DDE
180 DDT
181 Dieldrin
182 Endosulfan I
183 Endosulfan II
184 Endrin
185 Endrin aldehyde
186 Heptachlor
187 Heptachlor epoxide
188 Isodrin
189 Kepone
190 Hehoxychlor
191 Toxaphene
Phenoxyacetic Acid Herbicides
192 2,4-Dichlorophenoxyacetic acid
193 Silvex
194 2,4, 5-T
Organophosphorous Insecticides
195 Disulfoton
196 Famphur
197 Methyl parathion
198 Paration
199 Phorate
PCBs
200 Aroclor 1016
201 Aroclor 1221
202 Aroclor 1232
Untreated
K103
(mg/l)

NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA

NA
NA
NA

NA
NA
NA
NA
NA

ND
ND
ND
Untreated
K104
(mg/l)

NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA

NA
NA
NA

NA
NA
NA
NA
NA

ND
ND
ND
Treated
K103/K104
(mg/l)

NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA

NA
NA
NA

NA
NA
NA
NA
NA

ND
ND
ND
ND - Not  detected
NA - Not  analyzed
                                              5-9
Rev.  3
-------
TABLE 5-1  BOAT List Constituents in Untreated and Treated Waste (Continued)
Parameter
PCBs (continued)
203 Aroclor 1242
204 Aroclor 1248
205 Aroclor 1254
206 Aroclor 1260
Pi ox ins and Furans
207 Hexachlorodibenzo-p-dioxins
208 Hexachlorodibenzofuran
209 Pentachlorodibenzo-p-dioxins
210 Pentachlorodibenzofuran
211 Tetrachlorodibenzo-p-dioxins
212 Tetrachlorodibenzofuran
213 2,3,7,8-Tetrachlorodibenzo-p-dioxin
Untreated
K103
(mg/l)

ND
NO
NO
ND

ND
ND
ND
ND
ND
ND
ND
Untreated
K104
(mg/D

ND
ND
ND
ND

ND
ND
ND
ND
ND
MD
ND
Treated
K103/K104
(mg/l)

ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
ND - Not detected
                                            5-10
Rev.  3
-------
Since the waste codes K103 and K104 are mixed before the steam

stripping step, the analytical data for the treated waste are the

same for both waste codes.




     The untreated and treated waste samples were not analyzed

for other classes of BOAT organics (organochlorine pesticides,

phenoxyacetic acid herbicides, and organophosphorus pesticides)

because there is no in-process source of these constituents and

because of the extreme unlikelihood of finding these constituents

at treatable levels in the waste.




5.2  Determination of Classes of Constituents




     The BOAT list constituents in waste codes K103 and K104

belong to the following four classes: volatiles, semivolatiles,

metals, and inorganics (See Table 5-1).   Two volatile

constituents, benzene and trichloromonofluoromethane, were

detected.  Four semivolatile constituents, aniline,

2,4-dinitrophenol, nitrobenzene, and phenol were also detected.

Six metal constituents were also detected: arsenic, chromium,

lead, nickel, vanadium, and zinc.  The inorganic pollutants

detected were cyanide, fluoride, and sulfide.



                                         V-
     The metal constituents were present in untreatable

concentrations in the untreated waste codes K103 and K104.  None

of the metals in either untreated K103 or untreated K104 were
                               5-11                         Rev. 3
-------
detected at a concentration level higher than 1 mg/1.   Also, by



comparing the concentration of metals in the untreated and



treated waste for both waste codes K103 and K104,  the Agency



concluded that metals were not substantially treated.   For a



discussion of how the Agency decides when treatment is



substantial, see Section 1 of this background document.







     The BOAT metal constituents in K103 and K104 were not



present at treatable levels in the waste.  Therefore,  metals were



eliminated as a class of BDAT list constituents to be regulated



in waste codes K103 and K104.  However, the remaining three



classes of pollutants, namely, volatiles, semivolatiles, and



inorganics, were generally present at treatable concentration



levels in the untreated wastes and were judged to be



substantially treated when the untreated and treated constituent



data were compared for both waste codes.







5.3  Selecting the Regulated Constituents







     The Agency evaluated the analytical data for each



constituent to determine if the constituent should be selected



for regulation.  In general, the Agency was guided by the



criteria for selecting regulated constituents as described in



Section 1 of this background document.
                               5-12                         Rev. 3
-------
     The rationale for selecting the regulated constituents from

the four classes of constituents is presented below.




     Volatiles




     Benzene was present in significant concentrations in both

the untreated K103 and untreated K104 streams.  Benzene was

selected as a regulated constituent for waste codes K103 and K104

because it was substantially treated in both waste codes. The

benzene concentration in untreated K103 and untreated K104 was

reduced by the treatment system to below treatable levels.




     Trichloromonofluoromethane was not detected in either

untreated K103 or untreated K104,  but was detected in the treated

waste.  Although this compound was reported as not detected in

the untreated waste, the Agency has judged that it was present,

but was masked due to high concentrations of aniline and

nitrobenzene.  The Agency believes that effective treatment of

benzene will effectively treat trichloromonofluoromethane as

well.  Trichloromonofluoromethane is less soluble in water than

benzene, and is soluble in nitrobenzene.  This indicates that

trichloromonofluoromethane will also be effectively treated by

the solvent extraction step of the treatment system.
                                         v
Trichloromonofluoromethane has a higher vapor pressure than

benzene at 40°C, which indicates that trichloromonofluoromethane

will be effectively treated by the steam stripping step of the





                               5-13                         Rev. 3
-------
treatment system. As a result, trichloromonofluoromethane was not

selected as a regulated constituent for either waste code K103 or

waste code K104, because treatment for benzene will also treat

trichloromonofluoromethane.




     Semivolatiles




     Aniline was detected in untreated K103 at high concentration

levels.  Aniline was reported as not detected in untreated K104

but it was found in the treated waste at low concentration

levels.  Based on data analysis, the concentration of aniline in

the untreated K103 waste was substantially reduced (to be below

treatable levels) by the treatment system.  The Agency assumes

aniline was not detected in untreated K104 because the Practical

Quantification Levels were high due to matrix interferences.  The

Agency believes that aniline was present in untreated K104 and

that it was effectively treated by the treatment system.  As a

result, aniline was selected as a regulated constituent for both

waste codes K103 and K104.




     The BOAT list constituent 2,4-dinitrophenol was not detected

in either untreated K103 or untreated K104.  It was, however,

detected in the treated waste.  The Agency assumes that
                                        V
2,4-dinitrophenol was not detected in both untreated K103 and

untreated K104 because the Practical Quantification Levels were

high (see Appendix C) due to matrix interferences.  The Agency
                               5-14                         Rev. 3
-------
believes that 2,4-dinitrophenol was present in both untreated

K103 and untreated K104 and that it was effectively treated by

the treatment system.  As a result, 2,4-dinitrophenol was

selected as a regulated constituent for both waste codes K103 and

K104.




     Nitrobenzene was not detected in untreated K103.  It was

detected in untreated K104, and it was not detected in the

treated waste.  The concentration of nitrobenzene in untreated

K104 was substantially reduced by the treatment system.  The

Agency assumes that nitrobenzene was not detected in untreated

K103 because the Practical Quantification Levels were high (see

Appendix C) due to matrix interferences.  The Agency believes

that nitrobenzene was present in untreated K103 and that it was

effectively treated by the treatment system.  As a result,

nitrobenzene was selected as a regulated constituent for both


waste codes K103 and K104.




     Phenol was not detected in either untreated K103 or

untreated K104.  It was detected, however, in the treated waste.

The Agency assumes that phenol was not detected in both untreated

K103 and untreated K104 because the Practical Quantification

Levels were high (see Appendix C) due to matrix interferences.
                                         V
The Agency believes that phenol was present in both untreated


K103 and untreated K104 and that it was effectively treated by
                              5-15                         Rev. 3
-------
the treatment system.  As a result, phenol was selected as a

regulated constituent for both waste codes K103 and K104.




     Inorganics




     Cyanide was detected in untreated K103 and untreated K104,

and also in the treated waste.  Because the concentration of

cyanide in untreated K103 increased when the waste was treated,

the Agency concluded that cyanide in untreated K103 was not


effectively treated.  This apparent increase in cyanide

concentration for waste code K103 was thought to be due to the

mixing with waste code K104.  The cyanide concentration was

higher in untreated K104 than in untreated K103.  The

concentration of cyanide in untreated K104 was substantially

reduced by the treatment system.  Therefore, the Agency believes


that cyanide in untreated K104 was effectively treated by the

treatment system.  As a result, the Agency selected cyanide as a


regulated constituent for K104 but not for K103.




     Fluoride was not detected in either untreated K103 or

untreated K104.  It was, however, detected in the treated waste.

The Agency has judged that fluoride was present in both untreated


K103 and untreated K104 at concentration levels below the
                                         *•
Practical Quantification Level for the untreated waste matrix and

that it was not effectively treated by the treatment system.  As
                               5-16                        Rev. 3
-------
a result, fluoride was not selected as a regulated constituent

for either waste code K103 or waste code K104.



     Sulfide was detected in untreated K103, but was not detected

in either untreated K104 or in the treated waste. The Agency

recognizes that the sulfide concentration was diminished in the

treated waste, but considers this an incidental treatment since

the treatment technology tested is not demonstrated for the

treatment of sulfides.  As a result, sulfide was not selected as

a regulated constituent for either waste code K103 or waste code

K104.



     The regulated constituents for K103 are as follows:

     o    benzene
     o    aniline
     o    2,4-dinitrophenol
     o    nitrobenzene
     o    phenol


     The regulated constituents for K104 are as follows:

     o    benzene
     o    aniline
     o    2,4-dinitrophenol
     o    nitrobenzene
     o    phenol
     o    total cyanides


     For the nonwastewater forms of K103 and K104, the same BDAT

list constituents were chosen for regulation as shown above for

wastewaters.  This was done because the Agency did not have any

data available for determining the concentration of BDAT list

constituents in the nonwastewaters.



                               5-17                         Rev. 3
-------
           6.  CALCULATION OF BOAT TREATMENT STANDARDS







     In this section, the actual treatment standards for waste



codes K103 and K104 are presented.  These standards were



calculated based on the performance of the demonstrated treatment



system which was determined by the Agency to be the best for



treating both waste codes.  In Section 4, BOAT for the wastewater



forms of waste codes K103 and K104 was determined to be



liquid/liquid extraction followed by steam stripping and



activated carbon adsorption.  BOAT for the nonwastewater forms of



K103 and K104 was determined to be incineration.  The previous



section identified the constituents to be regulated for the



wastewater and nonwastewater forms of K103 and K104 wastes.







     As discussed in Section 1, the Agency calculated the BOAT



treatment standards for waste codes K103 and K104 by following a



four-step procedure: (1) editing the data; (2) correcting the



remaining data for analytical interference; (3) calculating



adjustment factors  (variability factors) to account for process



variability; and (4) calculating the actual treatment standards



using variability factors and average treatment values.  The four



steps in this procedure are discussed in detail in Sections 6.1



through 6.4.
                               6-1                         Rev. 3
-------
6.1  Editing the Data




     Five sets of treatment data for waste codes K103 and K104

were collected by the Agency at one facility which operated a

treatment system consisting of liquid/liquid extraction followed

by steam stripping and activated carbon adsorption.  The Agency

evaluated the five data sets to determine if the treatment system

was well operated at the time of the sampling visit.  The Agency

eliminated one data set, sample set #3, because the treatment

system was not well operated when the samples were collected  (as

discussed in Section 5).  For further details on the five data

sets, see the Onsite Engineering Report for K103 and K104.  The

remaining four data sets were used to calculate treatment

standards.




     Toxic Characteristic Leaching Procedure (TCLP) data were not

used in setting treatment standards for waste codes K103 and K104

because metals were not one of the classes of BOAT list

constituents identified for regulation (see Section 5 for further

details). For a discussion on the use of TCLP data in setting

treatment standards, refer to Section 1 of this background

document.



                                         V
     In instances where a selected constituent was not detected

in the treated waste, the treated value for that constituent was

assumed to be the Practical Quantification Level.  This was the
                               6-2                         Rev. 3
-------
case for the following constituents: (1) benzene in sample set



#2; (2) aniline in sample sets #1, #2, and #4;  (3) nitrobenzene



in sample sets #1, #2, #4, and #5; (4) phenol in sample sets #1,



#2, and #4.  Analytical values for the treated waste are



presented in Section 3, Tables 3-1 through 3-5 of this report.







6.2  Correcting the Remaining Data







     Data values for the constituents selected for regulation



were taken from the four data sets (sample sets I, 2, 4 and 5).



These values were corrected in order to take into account



analytical interferences associated with the chemical make-up of



the treated sample.  This was accomplished by calculating an



accuracy factor from the percent recoveries for each selected



constituent.  The reciprocal of the lower of the two recovery



values divided by 100, yields the accuracy factor.  The corrected



concentration for each sample set is obtained by multiplying the



accuracy factor by the uncorrected data value.  The calculation



of recovery values is described in Section 1 of this background



document.  The actual recovery values and accuracy factors for



the selected constituents are presented in Appendix E.







     The accuracy factors calculated for the selected



constituents varied from a high value of 4.76 for phenol to a low



value of 0.87 for nitrobenzene.  The corrected concentration



values for the selected constituents are shown for the four data
                               6-3                         Rev. 3
-------
sets in Table 6-1.  These corrected concentration values were

obtained by multiplying the accuracy factors (Appendix E) by the

concentration values for the selected constituents in the treated

waste.  An arithmetic average value, representing the treated

waste concentration, was calculated for each selected constituent

from the four corrected values.  These averages are presented in

Table 6-1.




6.3  Calculating Variability Factors




     It is expected that in normal operation of a well-designed

and well-operated treatment system there will be some variability

in performance.  Based on the test data, a measure of this

variability is expressed by the variability factor (see Appendix

A).  These factors were calculated for each of the selected

regulated constituents.  The methodology for calculating

variability factors is explained in Appendix A of this report.

Table 6-1 presents the results of calculations for the selected

constituents.  Appendix D of this report shows how the actual

values in Table 6-1 were calculated.




     The variability factors calculated for the selected

constituents vary from a high value of 15.40 for aniline to a low
                                        *
value of 1.65 for 2,4-dinitrophenol.  A variability factor of 1.0

represents test data from a process measured without variation

and analytical interferences.  Nitrobenzene was not detected in
                               6-4                         Rev. 3
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the treated waste, and concentration values for the treated waste

were set at the Practical Quantification Level for nitrobenzene.

This resulted in no apparent variation among the treated values

and a calculated variability factor of 1.0.  Instead of using the

calculated value of 1.0, the variability factor for nitrobenzene

was fixed at 2.8 as justified in Appendix D of this document.



6.4  Calculating the Treatment Standards



     The treatment standards for the selected constituents were

calculated by multiplying the variability factors by the average

concentration values for the treated waste.  The treatment

standards are presented in Table 6-1.  Standards were calculated

for wastewaters only.  The treatment standards for K103 and K104

nonwastewaters are transferred from the treatment tests of K019

and K048/K051 wastes.



     The BDAT Wastewater Treatment Standard for waste code K103

is as follows:



  Constituent                 Total Composition (mg/1)

Benzene                               0.147
Aniline                               4.450
2,4-Dinitrophenol                     0.613
Nitrobenzene                          0.Q7 3
Phenol                                1.391
                               6-6                         Rev. 3
-------
     The BOAT Wastewater Treatment Standard for waste code K104

is as follows:



  Constituent                 Total Composition (inq/1)

Benzene                               0.147
Aniline                               4.450
2,4-Dinitrophenol                     0.613
Nitrobenzene                          0.073
Phenol                                1.391
Total Cyanides (CN)                   2.683



     The treatment standards for waste codes K103 and K104 vary

from 4.45 mg/1 for aniline to 0.073 mg/1 for nitrobenzene.



     Nonwastewater treatment standards for waste codes K103 and

and K104 were also determined by the Agency.  These treatment

standards apply to the spent carbon from the carbon adsorber;

these treatment standards do not apply to the nitrobenzene

solvent from the liquid/liquid extractor because the Agency

believes that no ash is formed when this stream is incinerated.



     No performance data were available for the treatment of K103

and K104 nonwastewaters.  The Agency therefore decided to

transfer treatment standards from the treatment of wastes which

were determined to be similar to K103 and K104 nonwastewaters

based on waste characteristics affecting „performance.  The

nonwastewater treatment standards for waste codes K103 and K104

were transferred from treatment data for wastes K019 and

K048/K051.  The thermal conductivities of wastes K019, K048, and



                               6-7                         Rev. 3
-------
K051 were compared with the thermal conductivities of waste codes

K103 and K104.  Waste K019 was selected for transferring

treatment standards to wastes K103 and K104 because its thermal

conductivity was lower than that of both wastes K103 and K104.

The treated waste concentrations and treatment standards for K019

are presented in Table 6-2.  The boiling points of the selected

constituents in waste codes K103 and K104 were compared to the

boiling points of the regulated constituents in waste code K019.

Constituents were matched as closely as possible on the basis of

the boiling point (see Table 6-2).



     Chlorinated organic constituents in K019 with three or more

chlorine atoms in their structure were eliminated from

consideration for this matching.  All chlorinated organics with

three or more chlorine atoms were below detectable levels in

treated K019.  The treated concentrations were therefore set at

the detection limit for these constituents.  However, the

detection limits for these constituents were abnormally high in

treated K019 due to matrix interferences, leading to high

treatment standards.  Therefore, chlorinated organic constituents

with three or more chlorine atoms were not considered when

matching constituents from K103 and K104 with those from K019.

The remaining constituents in K019 were matched as closely as
                                         V
possible with those in K103 and K104 on the basis of boiling
                               6-8                         Rev. 3
-------









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point.1  Treatment standards were then transferred from waste

code K019 to the matched constituent.  Cyanide treatment

standards were transferred from the treatment of K048/K051, since

cyanide was not present in K019 waste.



     The BDAT nonwastewater treatment standards for waste codes

K103 and K104 are as follows:
Total Composition
Constituent
Benzene
Aniline
2,4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides  (CN)
NR - Not regulated for this waste code.
                    K104

                    5.96
                    5.44
                    5.44
                    5.44
                    5.44
                    1.48
1.   The removal of highly chlorinated organic constituents in
     K019 from consideration for transfer affected the treatment
     standards for the following constituents in K103 and K104:
     nitrobenzene (naphthalene was used rather than 1,2,4-tri-
     chlorobenzene), aniline, and phenol (naphthalene was used
     rather than hexachloroethane or 1,2,4-trichlorobenzene).
                               6-10
                             Rev. 3
-------
                         7.   CONCLUSIONS




     The Agency has proposed treatment standards for waste codes

K103 and K104 generated by the nitrobenzene/aniline industry.

Standards for wastewater and nonwastewater forms of these wastes

are presented in Tables 7-1 and 7-2 respectively.




     The treatment standards proposed for waste code K103 and

K104 have been developed consistent with EPA's promulgated

methodology for BOAT (November 7, 1986, 51 FR 40572).  Both waste

codes are generated by the treatment of process wastewaters from


the nitrobenzene/aniline industry.  Based on a careful review of

available data for the industrial processes which generate these

wastes and all available data characterizing these wastes, the

Agency has determined that these two waste codes represent a

separate waste treatability group.  Wastes in this treatability

group are primarily comprised of water, with nitrobenzene or

aniline present in smaller but significant quantities.  Although

the concentrations of specific constituents will vary from

facility to facility, all of the wastes are expected to contain

similar BDAT list organics and are expected to be treatable to

the same levels using the same technology.



                                         V-
     The BDAT list constituents generally present in wastes of

this treatability group are benzene, aniline, 2,4-dinitrophenol,


nitrobenzene, phenol, and cyanides.  Additionally the Agency
                               7-1                         Rev. 3
-------
TABLE 7-1  BOAT TREATMENT STANDARDS FOR WASTEWATER:  K103 AND
             K104 WASTES
Regulated Constituents             Total Composition  (mg/1)
                                   K103           K104
Benzene
Aniline
2 , 4-Dinitrophenol
Nitrobenzene
Phenol
Total Cyanides
0.147
4.450
0.613
0.073
1.391
NR
0.147
4.450
0.613
0.073
1.391
2.683
NR - Not regulated for this waste code.
TABLE 7-2  BOAT TREATMENT STANDARDS FOR NONWASTEWATER:
             K103 AND K104 WASTES
Regulated Constituents             Total Composition  (mg/kg)
                                   K103           K104

Benzene                            5.96           5.96
Aniline                            5.44           5.44
2,4-Dinitrophenol                  5.44           5.44
Nitrobenzene                       5.44           5.44
Phenol                             5.44           5.44
Total Cyanides                      NR            1.48
NR - Not regulated for this waste code.
                               7-2                          Rev.  3
-------
expects that these wastes could be mixed together prior to

treatment.  As a result, EPA has examined the sources of the

wastes, applicable technologies, and waste treatment performance

in order to support a single regulatory approach for these six

waste constituents.  Through available data bases, the Agency has

identified the following demonstrated technologies for treatment

of constituents present in the wastes which are part of this

treatability group: solvent (liquid/liquid) extraction, steam

stripping, activated carbon adsorption, and biological treatment.




     In the development of treatment standards for these wastes,

the Agency examined all available treatment data.  The Agency

also conducted performance tests on a commercial scale treatment

system consisting of liquid/liquid extraction followed by steam

stripping and activated carbon adsorption for waste codes K103

and K104.  Design and operating data collected during the testing

of the treatment system indicate that the treatment system was

properly operated during four of the five sample sets.

Accordingly, the treatment performance data from four sample sets

were used in the development of the BOAT treatment standards.




     Two categories of treatment standards were developed for

wastes in the K103 and K104 treatability group: wastewater and
                                        *•
nonwastewater wastes.  (For the purpose of the land disposal

restrictions rule, wastewaters are defined as wastes containing
                               7-3                         Rev. 3
-------
less than 1% by weight filterable solids and less than 4% by



weight total organic carbon.  For K103 and K104 wastes, this



definition was amended to include wastewaters with a TOC content



up to 4%).








     BOAT for the wastewater forms of waste codes K103 and K104



was determined to be liquid/liquid extraction followed by steam



stripping and activated carbon adsorption.  This was based on a



statistical comparison of the Agency's test and performance data



from this treatment train to other available treatment data.  The



wastewater treatment standards for waste codes K103 and K104 are



based on EPA's test of liquid/liquid extraction followed by steam



stripping and activated carbon adsorption.








     Two nonwastewater forms of waste codes K103 and K104 were



identified by the Agency as spent carbon from the activated



carbon adsorber and nitrobenzene solvent from the nitrobenzene



liquid/liquid extractor.







     Incineration was determined to be BOAT for the nonwastewater



forms of wastes K103 and K104.  Nonwastewater treatment standards



for K103 and K104 are based on a transfer of treatment data from



K019 and K048/K051 wastes.  BOAT for wastes K019 and K048/K051



was determined to be rotary kiln incineration.  Treatment data



for BDAT list organics were transferred from waste KOI9 based on



a comparison of the thermal conductivities between waste code
                               7-4                         Rev. 3
-------
K019 and waste codes K103 and K104.  Data were transferred for



constituents selected for regulation on a constituent by



constituent basis.  This was done by matching constituents on the



basis of boiling points.  Treatment standards for cyanide were



transferred from the treatment of K048/K051, since cyanide was



not present in K019 waste.








     Nonwastewater standards are established only for the spent



carbon from the activated carbon adsorber because the Agency



believes that the incineration of the nitrobenzene solvent from



the nitrobenzene liquid/liquid extractor will not produce ash.



The transfer of data for these nonwastewaters was determined to



be appropriate due to the similarity in physical and chemical



composition of the wastes such that the wastes would be expected



to be treated to similar levels by the same technology.








     Regulated constituents were selected on the basis of



substantial treatment, which was determined by comparing the



constituent concentrations detected in the untreated and treated



wastes.  All waste characterization data and applicable treatment



data consistent with the type and quality of data needed by the



Agency in this program were used to make this determination.  For



waste codes K103 and K104, the regulated constituents also



represent the BDAT list constituents present at the highest



concentrations.  However, if the performance data for the



technology selected as BDAT indicated that the constituent was
                               7-5                         Rev. 3
-------
not significantly treated,  then that constituent was not



regulated.  Some constituents present at treatable concentrations



in the untreated waste were not regulated if it was determined



that they would be adequately controlled by regulation of another



constituent.







     Treatment standards for these wastes were derived after



correction of laboratory data to account for recovery



(Section 6). Subsequently,  the mean of the corrected data points



was multiplied by a variability factor to derive the standards.



The variability factor corrects the lab data for reasonable



variations measured in the treatment process and imprecision in



sampling and analytical methods. Variability factors were



determined using a statistical method which accounts for



variability in the results for a number of data points for a



given constituent.  A variability factor of 2.8 was chosen for



constituents for which a specific variability factor could not be



calculated (See Appendix A for justification).







     Wastewater and nonwastewater forms of waste codes K103 and



K104 may be land disposed if they meet the concentration



standards at the point of disposal.  The BDAT technology upon



which the treatment standards are based (liquid/liquid extraction



followed by steam stripping and activated carbon adsorption for



wastewater, and incineration for nonwastewater) need not be



specifically utilized prior to land disposal, provided that the
                               7-6                         Rev. 3
-------
actual technology utilized meets the standard, does not involve



dilution or other methods deemed unacceptable by the Agency, and



does not pose a greater risk to human health and the environment



than land disposal.







     These standards become effective as of August 8, 1988, as



per the schedule set forth in 40 CFR 268.10.  The Agency



estimates that there is a lack of nationwide treatment capacity



at this time for the nonwastewater forms of waste codes K103 and



K104.  Therefore, the Agency has proposed to grant a 2-year



nationwide variance to the effective date of the land disposal



ban for these wastes.  A detailed discussion of the Agency's



determination that a lack of nationwide incineration capacity



exists is presented in the Capacity Background Document which is



available in the Administrative Record for the First Sixths'



Rule.







     Consistent with Executive Order 12291, EPA prepared a



regulatory impact analysis (RIA)  to assess the economic effect of



compliance with this proposed rule.  The RIA prepared for this



proposal rule is available in the Administrative Record for the



First Sixths' Rule.
                               7-7                         Rev. 3
-------
                            REFERENCES


Ackerman D.G., J.F. McGaughey, D.E. Wagoner, "At Sea Incineration
     of PCB-Containing Wastes on Board the M/T Vulcanus."  USEPA
     600/7-83-024, April 1983.

Authur D. Little, Inc. (1977).  "Physical, Chemical and
     Biological Treatment Techniques for Industrial Wastes."
     Vol. I - NTIS PB275-054.  pp. 1-1 to 1-18 and 1-37 to 1-41.

Bonner T.A.,  et al., Engineering Handbook for Hazardous Waste
     Incineration.  SW889.  Prepared by Monsanto Research
     Corporation for U.S. EPA, NTIS PB 81-248163. June 1981.

De Renzo, D.J.  (editor).   (1978).  Unit Operations for Treatment
     of Hazardous Industrial Wastes.  Noyes Data Corporation,
     Park Ridge, New Jersey.

Enckenfelder, W., et al.   (September 2,1985).  "Wastewater
     Treatment."   Chemical Engineering.

Gallacher, Lawrence V.  (February 1981).   "Liquid Ion Exchange in
     Metal Recovery and Recycling."  3rd Conference on Advanced
     Pollution Control for the Metal Finishing Industry.  U.S.
     EPA 600/2-81-028.  pp. 39-41.

GCA Corp.  (October 1984).  Technical Assessment of Treatment
     Alternatives for Wastes Containing Halogenated Organics.
     Prepared for USEPA,  Contract 68-01-6871.  pp. 150-160.

Hackman, Ellsworth.  (1978).  Toxic Organic Chemicals.
     Destruction and Waste Treatment.  Noyes Data Corporation,
     Park Ridge, New Jersey, pp. 109-111.

Hanson, Carl.  (August 26, 1968).  "Solvent Extraction Theory,
     Equipment, Commercial Operations,  and Economics."  Chemical
     Engineering,  p. 81.

Hutchins, R.   (1979) .  "Activated Carbon Systems for Separation
     of Liquids."  pp. 1-415 through 1-486 as published in
     Handbook of Separation Techniques for Chemical Engineers.
     Philip A. Schweitzer (editor).  McGraw-Hill.

Humphrey, Jimmy L., J. Antonia Rocha, and James R. Fair.
     (September 17, 1984).  "The Essentials of Extraction."
     Chemical Engineering,  pp. 76-95.

Kirk & Othmer.  (1965).   Encyclopedia of Chemical Technology.
     2nd ed., Vol. 7, John Wiley and Sons, New York.  pp. 204-
     248.
                                                           Rev. 3
-------
                      REFERENCES  (Continued)


Kirk & Othmer.  Encyclopedia of Chemical Technology.  Volume 2
     (p. 37-361), Vol. 15 (p. 916-925).

Ku, W. and Peters, R.W. (May 1987).  "Innovative Uses or Carbon
     Adsorption of Heavy Metals from Plating Wastewaters:
     I. Activated Carbon Polishing Treatment."  Environmental
     Progress.

Lo, Teh C., Malcolm H. I. Baird,  and Carl Manson (editors). 1983.
     Handbook of Solvent Extraction.  John Wiley and Sons.  New
     York. pp. 53-89.

McCabe, Warren L., Julian C. Smith, and Peter Harriot.   (1985).
     Unit Operations of Chemical Engineering.  McGraw-Hill Book
     Company, New York.  pp. 533-606.

Metcalf and Eddy Inc.  (1985).   "Briefing, Technologies
     Applicable to Hazardous Waste."  Prepared for USEPA, ORD,
     HWERL.  Section 2.13.

Mitre Corp.  "Guidance Manual for Waste Incinerator Permits."
     NTIS PB84-100577.  July 1983.

Novak R.G., W.L. Troxler, T.H.  Dehnke, "Recovering Energy from
     Hazardous Waste Incineration."  Chemical Engineering
     Progress 91:146  (1984).

Oppelt E.T., "Incineration of Hazardous Waste."  JAPCA, Volume
     37, No. 5.  May 1987.

Patterson, J. (1985).  Industrial Wastewater Treatment
     Technology.  2nd ed., Butterworth Pub. pp. 329-340.

Perry, Robert H. and Cecil H. Chilton.  (1973).  Chemical
     Engineer's Handbook. 5th edition.  McGraw-Hill Book Company,
     New York. pp. 13-1 to 13-60 and pp. 15-1 to 15-24.

Rose, L.M.   (1985).  Distillation Design in Practice.  Elsevier,
     New York. pp. 1-307.

Santoleri J.J., "Energy Recovery-A By-Product of Hazardous Waste
     Incineration Systems."  In Proceedings of the 15th Mid-
     Atlantic Industrial Waste Conference, on Toxic and Hazardous
     Waste, 1983.

SRI.   (1985).  Stanford Research Institute.  Chemical Economics
     Handbook (CEH). Menlo Park.  California.
                                                           Rev. 3
-------
                      REFERENCES (Continued)


Touhill, Shuckrow & Assoc.  (February 1981).  "Concentration
     Technologies for Hazardous Aqueous Waste Treatment."  NTIS
     PB81-150583. pp. 53-55.

U. S. Environmental Protection Agency.  (May 1981).
     Identification and Listing Hazardous Waste under RCRA.^
     Subtitle C. Section 3001. Background  Document.

U.S.  EPA.  (1987).  Onsite Engineering Report of Treatment
     Technology Performance and Operation for E.I, du Pont de
     Nemours & Co.. Inc. - Beaumont. TX.

USEPA   (October 1973).  Process Design Manual for Carbon
     Adsorption.  NTIS PB227-157.  pp. 3-21 and 53.

USEPA   (1986).  Best Demonstrated Available Technology  (BOAT)
     Background  Document for F001-F005 Spent Solvents, Vol. 1.
     EPA/530-SW-86-056, November, 1986.

Van Winkle, Matthew.  (1967).  Distillation.  McGraw-Hill Book
     Company,  New York.  pp. 1-684.

Versar  (1985).  Versar, Inc.  An Overview of Carbon Adsorption.
     Draft Final Report.  U.S. Environmental Protection Agency:
     Exposure Evaluation Division Office of Toxic Substances,
     Washington, D.C.  EPA Contract No. 68-02-3968, Task No. 58.

Vogel G., et al., "Incineration and Cement Kiln Capacity for
     Hazardous Waste Treatment."  In Proceedings of the 12th
     Annual Research Symposium.  Incineration and Treatment of
     Hazardous Wastes.  Cincinnati, Ohio.   April 1986.

Water Chemical Corporation. (August 1984).  Process Design Manual
     of Stripping of Organics.  NTIS PB84-232628.  Prepared for
     the Industrial Environmental Research Laboratory Office of
     Research and Development, U.S. Environmental Protection
     Agency,  pp. 1-1 to F4.
                                                           Rev. 3
-------
                APPENDIX A - STATISTICAL ANALYSIS




A.1  F Value Determination for ANOVA Test




     As noted earlier in Section 1.0, EPA is using the


statistical method known as analysis of variance in the

determination of the level of performance that represents "best"


treatment where more than one technology is demonstrated.  This


method provides a measure of the differences between data sets.


If the differences are not statistically significant, the data

sets are said to be homogeneous.




     If the Agency found that the levels of performance for one

or more technologies are not statistically different (i.e., the


data sets are homogeneous), EPA would average the long term


performance values achieved by each technology and then multiply


this value by the largest variability factor associated with any


of the acceptable technologies.  If EPA found that one technology

performs significantly better (i.e., the data sets are not

homogeneous),  BOAT would be the level of performance achieved by


the best technology multiplied by its variability factor.




     To determine whether any or all of the treatment performance
                                        
-------
values are available in most statistics texts (see, for example,

Statistical Concepts and Methods by Bhattacharyya and Johnson,

1977, John Wiley Publications, New York).



     Where the F value is less than the critical value, all

treatment data sets are homogeneous.  If the F value exceeds the

critical value, it is necessary to perform a "pair wise F" test

to determine if any of the sets are homogeneous.  The "pair wise

F" test must be done for all of the various combinations of data

sets using the same method and equation as the general F test.



     The F value is calculated as follows:



     (i)  All data are natural logtransformed.

     (ii)  The sum of the data points for each data set is

            computed (T.).

     (iii)  The statistical parameter known as the sum of the

            squares between data sets (SSB) is computed:
     SSB •
A
k
I
1-1
'^_'
ni



_

r


k
i-1 Tl

N
Z


     where:
     k  = number of treatment technologies
     n. = number of data points for technology i
     N  = number of data points for all technologies
     T. = sum of natural logtransformed data points for each
          technology.
                           Appendix A-2
Rev. 3
-------
(iv)  The sum of the squares within data sets  (SSW)  is
      computed:
      SSW =
• k
I
j;
x2,
,j
k
- I
1-1
'!L
ni .
where:
x.  . = the natural logtransformed observations  (j)  for
  '-1   treatment technology  (i) .



(v)  The degrees of freedom  corresponding to SSB and  SSW  are

     calculated.  For SSB, the  degree of freedom is given by

     k-1.  For SSW, the degree  of freedom is given by N-k.



(vi)  Using the above parameters, the F value is calculated

     as follows:
where:


MSB = SSB/(k-1) and

MSW = SSW/(N-k).
                              MSB
                          F = MSW
                      Appendix A-3
Rev. 3
-------
     A computational table summarizing the above parameters is
shown below.


               Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
K-l
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F
MSB/MSW
     Below are three examples of the ANOVA calculation.  The

first two represent treatment by different technologies that

achieve statistically similar treatment; the last example

represents a case where one technology achieves significantly

better treatment than the other technology.
                           Appendix A-4
Rev. 3
-------
                   Table A-l
F Distribution at the 95 Percent Confidence Level
                      ro n
Denominator
degrees ol
freedom 1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
40
60
>20
QO
16T 4
1851
10 13
7 71
661
599
559
5,32
5.12
496
484
475
467
460
454
449
445
441
438
435
432
430
428
426
424
423
421
420
418
417
408
400
392
3.84
2
1995
1900
955
694
579
514
4 74
446
426
4 10
398
389
381
374
368
363
359
355
352
349
347
344
3.42
340
339
337
335
334
333
3.32
323
3.15
3.07
3.00
3
2157
1916
923
659
541
476
435
407
3.86
3.71
359
349
341
334
329
324
320
316
313
310
307
305
303
301
299
298
296
295
2.93
292
2.84
2.76
2.68
2.60
Numerator degrees ol freedom
4567
2246
1925
912
639
5.19
453
412
3.84
363
348
336
3.26
3.18
311
306
301
296
293
290
287
284
282
280
2.78
276
274
273
271
2.70
269
2.61
253
245
2.37
2302
1930
901
626
5.05
439
397
3.69
3.48
3.33
3.20
311
3.03
2.96
290
2.85
281
2.77
274
2.71
2.68
266
2.64
262
260
259
257
256
255
253
2.45
237
229
2.21
2340
1933
894
616
495
428
3.87
358
337
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
266
2.63
260
2.57
2.55
2.53
251
249
247
246
2.45
243
242
2.34
225
2.17
2.10
236.8
1935
889
6.09
488
421
3.79
3.50
3.29
3.14
3.01
2.91
2.83
2.76
2.71
266
2.61
258
2.54
2.51
249
2.46
244
242
2.40
2.39
2.37
2.36
2.35
2.33
2.25
* 2.17
2.09
2.01
a
2389
1937
885
604
482
415
3.73
3.44
323
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.42
2.40
2.37
2.36
234
2.32
231
2.29
2.28
2.27
2.18
2.10
2.02
194
9
2405
1938
881
600
477
410
368
339
3.18
3.02
2.90
280
2.71
2.65
259
254
249
246
242
239
237
234
232
2.30
228
2.27
225
2.24
2.22
221
212
204
196
1 88
                   Appendix A-5
Rev.  3
-------
                                                       Example 1
                                                   Methytene Chloride
Steam stripping

Influent
(mg/l)
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4800.00
12100.00

Effluent
(mg/l)
10.00
10.00
10.00
12.00
10.00
10.00
10.00
10.00
10.00
10.00

In(effluent)

2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30

2
[ln(ef fluent)]

5.29
5.29
5.29
6.15
5.29
5.29
5.29
5.29
5.29
5.29


Influent
(mg/l)
1960.00
2568.00
1817.00
1640.00
3907.00





Biological treatment

Effluent In(effluent)
(mg/l)
10.00 2.30
10.00 2.30
10.00 2.30
26.00 3.26
10.00 2.30






2
[ln( effluent)]

5.29
5.29
5.29
10.63
5.29





Sun:
                              23.18
                                      53.76
                                                                                       12.46
                                                                                                          31.79
Sample Size:
    10           10
Mean:
  3669
       10.2
Standard Deviation:
  3328.67          .63

Variability Factor:
                 1.15
                      10
                               2.32
                                .06
                                                 2378
                                                  923.04
                                                                          13.2
                                                                          7.15
                                                                           2.48
                                                                                       2.49
                                                                                         .43
ANOVA Calculations:
 SSB
III!!
     f>i
            A
SSW <

MSB =  SSB/(k-1)

HSU =  SSW/(N-k)
                              ''

                 t    _
                i-l I n,
                                               Appendix  A-6
                                                                                          Rev.  3
-------
                                    Example 1   (continued)

F   = MSB/HSW

where:

k   = number of treatment  technologies

n.  = number of data points  for  technology  i

N   = nunber of natural  log  transformed data points for all technologies

T.  = sum of log transformed data points for each technology

X   = the nat.  log transformed observations (j) for treatment technology (i)
  i i
ni = 10, n  = 5,  N = 15,  k  =  2, T  = 23.18, T  = 12.46,  T = 35.64, T = 1270.21
T  = 537.31   T  = 155.25
cco
SSB
       537.31    155.25
         10
              1270.21

                15
0.10
SSWM53.76.31.79)-!537'31.155-25'
                            10
                                         0.77
MSB = 0.10/1  = 0.10

MSW = 0.77/13 = 0.06

      0.10
F  =
      0.06
1.67
                                   ANOVA Table
Degrees of
Source freedom
Between(B) 1
Within(U) 13

SS MS F
0.10 0.10 1.67
0.77 0.06
      The critical  value  of  the F test at the 0.05 significance level is 4.67.   Since the
      F value is less  than the critical value, the means are not significantly different
      (i.e.,  they are  homogeneous).                                       „

Note:   All calculations were rounded to two decimal places.  Results may differ
       depending upon  the number of decimal places used in each step of the calculations.
                                                  Appendix  A-7
                                                                                          Rev.  3
-------
                                                       Example 2
                                                   Trichloroethylene
Steam stripping

Influent
(mg/O
1650.00
5200.00
5000.00
1720.00
1560.00
10300.00
210.00
1600.00
204.00
160.00

Effluent
(mg/D
10.00
10.00
10.00
10.00
10.00
10.00
10.00
27.00
85.00
10.00

In(effluent)

2.30
2.30
2.30
2.30
2.30
2.30
2.30
3.30
4.44
2.30

2
[ln(ef fluent)]

5.29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Biological treatment

Influent
(mg/l)
200.00
224.00
134.00
150.00
484.00
163.00
182.00




Effluent
(mg/l)
10.00
10.00
10.00
10.00
16.25
10.00
10.00




ln( effluent)

2.30
2.30
2.30
2.30
2.79
2.30
2.30




2
[ln( effluent)]

5.29
5.29
5.29
5.29
7.78
5.29
5.29



Sum:
Sample Size:
     10          10
Mean:
   2760
        19.2
Standard Deviation:
   3209.6        23.7

Variability Factor:
                 3.70
                              26.14
                       10
2.61
                        .71
                                      72.92
220
                            120.5
                                          10.89
                2.36
                                                                   1.53
                                                        16.59
2.37
 .19
                                               39.52
ANOVA Calculations:
SSB
 U-
1=1   n,
ssw .

MSB = SSB/(k-1)

MSW = SSW/(N-k)
                        r  k
                                                Appendix  A-8
                                                                                           Rev.  3
-------
                                    Example 2  (continued)

f   = HSB/HSW

where:

k   = number of  treatment technologies

n.  = number of  data  points for technology i

N   = number of  data  points for all technologies

T.  = sum of natural  log transformed data points  for each technology

X   = the natural  log transformed observations  (j)  for treatment technology  (i)
M  = 10, N  = 7,  N  =  17, k = 2, T  = 26.14,  T  = 16.59, T = 42.73,  T = 1825.85. T  = 683.30,


^2 = 275.23

.S8 J683_30  +   275.MJ  _  1K5.B5             =  0_25
     i 10            7    j      17
SSW » (72.92 > 39.52, -   ""•'"  *  ""I         = 4.79
                        (   10        7

MSB = 0.25/1 = 0.25

MSW = 4.79/15 = 0.32

F = °'     = 0.78
    0.32

                                   ANOVA Table
Degrees of
Source freedom
Between(B) 1
Uithin(W) 15

SS MS F
0.25 0.25 0.78
4.79 0.32
      The critical value of the F test at the 0.05 significance level  is 4.54.  Since the
      F value is  less than the critical value,  the means are not significantly different
      (i.e.,  they are homogeneous).
Note:   All  calculations were rounded to two decimal places.  Results may differ
       depending upon the number of decimal places used in each step of the calculations.
                                                 Appendix  A-9                                  Rev.  3
-------
Example 3
Chlorobenzene
Activated sludge followed

Influent
(mg/l)
7200.00
6500.00
6075.00
3040.00




Effluent
(mg/l)
80.00
70.00
35.00
10.00



by carbon adsorption Biological treatment
2 	 '
In(effluent) [ln(eff luent)] Influent
(mg/l)
4.38 19.18 9206.00
4.25 18.06 16646.00
3.56 12.67 49775.00
2.30 5.29 14731.00
3159.00
6756.00
3040.00

Effluent
(mg/l)
1083.00
709.50
460.00
142.00
603.00
153.00
17.00

ln( effluent)

6.99
6.56
6.13
4.96
6.40
5.03
2.83

2
In [(effluent)]

48.86
43.03
37.58
24.60
40.96
25.30
8.01
Sum:
Sample Size:
     4           4
Mean:
   5703
                49
Standard Deviation:
   1835.4        32.24

Variability Factor:
                 7.00
                               14.49
                                               55.20
3.62
                                .95
14759
                         16311.86
452.5
                379.04
                                                                         15.79
                                                        38.90
                                                  228.34
5.56
                1.42
ANOVA Calculations:
SSB
              -
              "1
         z,   r,
ssw

MSB = SSB/(k-1)

MSU = SSW/(N-k)

F   = MSB/MSW
                         r  k

                              T,2
                                               Appendix  A-10
                                                                                                   Rev.   3
-------
                                    Example 3  (continued)
where,

k   = number of treatment  technologies
n.  = number of data points for technology i

N   = number of data points for all technologies
T.  = sum of natural log transformed data points for  each technology
X.. = the natural  log transformed observations (j)  for  treatment technology (i)


N  = 4, N = 7,  N = 11,  k = 2, T  = 14.49, T  = 38.90, T = 53.39, T = 2850.49,  T  = 209.96


I2 = 1513.21


SSB »l	  +  	   |  -                   =  9.52
                                11
=14.88
SSW - (55.20 * 228.34)  -
MSB = 9.52/1  = 9.52

MSW = 14.88/9 = 1.65

F = 9.52/1.65 = 5.77

                                   ANOVA Table
                   Degrees of
          Source    freedom               SS             MS
Between(B)
Uithin(U)
1
9
9.53
14.89
9.53
1.65
5.77
      The critical  value of the F test at  the 0.05 significance level is 5.12.   Since the
      F value is  larger than the critical  value,  the means are significantly different
      (i.e.,  they are heterogeneous).
Note:  All  calculations were rounded to two decimal places.  Results may differ  depending
       upon the  number of decimal places used  in each step of the calculations.
                                                Appendix A-ll                                  Rev.  3
-------
A.2.  Variability Factor

                                     C99

                               VF = Mean

     where:

      VF =   estimate of daily maximum variability factor
             determined from a sample population of daily data.
     C   =   Estimate of performance values for which 99 percent
             of the daily observations will be below.  C 9 is
             calculated using the following equation:
             C   = Exp(y +2.33 Sy) where y and Sy are the mean
             ana standard deviation, respectively, of the
             logtransformed data.
     Mean =  average of the individual performance values.
     EPA is establishing this figure as an instantaneous maximum

because the Agency believes that on a day-to-day basis the waste

should meet the applicable treatment standards.  In addition,

establishing this requirement makes it easier to check compliance

on a single day.  The 99th percentile is appropriate because it

accounts for almost all process variability.



     In several cases, all the results from analysis of the

residuals from BOAT treatment are found at concentrations less

than the detection limit.  In such cases, all the actual

concentration values are considered unknown and hence, cannot be

used to estimate the variability factor of the analytical

results.  Below is a description of EPA's, approach for

calculating the variability factor for such cases with all

concentrations below the detection limit.
                          Appendix A-12                    Rev. 3
-------
     It has been postulated as a general rule that a lognormal

distribution adequately describes the variation among

concentrations.  Therefore, the lognormal model has been used

routinely in the EPA development of numerous regulations in the

Effluent Guidelines program and is being used in the BDAT

program.  The variability factor (VF) was defined as the ratio of

the 99th percentile (Cgg) of the lognormal distribution to its

arithmetic mean (Mean).
           VF =     ^99                                        (1)
                   Mean

     The relationship between the parameters of the lognormal

distribution and the parameters of the normal distribution

created by taking the natural logarithms of the

lognormally-distributed concentrations can be found in most

mathematical statistics texts (see for example:  Distribution  in

Statistics-Volume 1 by Johnson and Kotz, 1970).  The mean of the

lognormal distribution can be expressed in terms of the mean (JJL )

and standard deviation ( Q- )  of the normal distribution as

follows:




         C9g    =  Exp ( JU  +  2.3340-)                        (2)


          Mean   =  Exp  ( Jj^  +   .54
-------
          VF = Exp  (2.33 d   -  .54cr2)                       (4)

     For residuals with concentrations that are not all below the

detection limit, the 99th percentile and the mean can be

estimated from the actual analytical data and accordingly, the

variability factor (VF) can be estimated using equation (1) .  For

residuals with concentrations that are below the detection limit,

the above equations can be used in conjunction with the

assumptions below to develop a variability factor.


Step 1: The actual concentrations follow a lognormal

distribution.  The upper limit (UL) is equal to the detection

limit.  The lower limit (LL) is assumed to be equal to one tenth

of the detection limit.  This assumption is based on the fact

that data from well-designed and well-operated treatment systems

generally falls within one order of magnitude.


Step 2: The natural logarithms of the concentrations have a

normal distribution with an upper limit equal to In (UL) and a

lower limit equal to In (LL) .


Step 3: The standard deviation (CT ) of the normal distribution

is approximated by
                                        *

    CT = [(In  (UL) - In (LL) ] /  [(2) (2.33)] = [ln(UL/LL)] /4.66

     when LL =  (0.1) (UL) then  
-------
Step 4: Substitution of the value from Step 3 in equation (4)



yields the variability factor, VF.








     VF = 2.8
                          Appendix A-15                    Rev. 3
-------
             APPENDIX B - ANALYSIS OF VARIANCE TESTS
ANOVA #1

Comparison  of L/L  Extraction  with L/L  Extraction  Followed by
Steam Stripping

Compare  sample point  SD-5  (Untreated Waste to  Steam Stripper)
with sample point SD-6 (Treated Waste From Steam Stripper)

Regulated Constituents:  Benzene
                         Nitrobenzene
                         2,4-Dinitrophenol
                         Phenol
                         Aniline
                         Cyanide


Regulated Constituents Present in Untreated Waste (SD-5):

                         Benzene
                         Nitrobenzene
                         Cyanide

Regulated Constituents Present in Treated Waste (SD-6):

                         Benzene
                         2,4-Dinitrophenol (*)
                         Cyanide


* -  An   ANOVA  analysis   could  not  be   completed   on  this
     constituent,  since  no  information  is  available  on  the
     concentration  of this  constituent   in  the  untreated waste
     (SD-5).
                          Appendix B -  1                    Rev. 3
-------
1)  Benzene (ug/1)
    AF = 1.32
Raw   SD-5
Corr. SD-5

Raw   SD-6
Corr. SD-6
170,000
224,400

  (5)
  6.6
2) Nitrobenzene (ug/1)
    AF = 0.87
Raw   SD-5
Corr. SD-5

Raw   SD-6
Corr. SD-6
3) Cyanide (mg/1)
    AF = 1.39
190,000
250,800

   8
 10.6
26,000
34,320

  (5)
  6.6
17,000
22,440

  (5)
  6.6
2.3X106
2.0X106
(3000)
2610
2.8X106
2.4X106
(3000)
2610
2.0X106
1.7X106
(1500)
1305
2.0X106
1.7X106
(3000)
2610
Raw   SD-5     4.36
Corr. SD-5     6.06

Raw   SD-6     4.77
Corr. SD-6     6.63
             3.45
             4.80

             3.87
             5.38
           2.54
           3.53

           2.08
           2.89
           2.27
           3.16

           1.70
           2.36
Note:     Numbers  in  parentheses indicate that  the compound was
          not detected  in this sample.   The detection limit has
          been  used  in  place  of  the  actual  value for  this
          compound.

(Above  raw values  are  taken  from  the EPA's  Onsite  Engineering
Report for K103 and K104. Tables 6-10 and 6-11).
                          Appendix B - 2
                                              Rev. 3
-------
1)  Benzene

          Treatment 1    Treatment 2    	x1—     	x2_
SSI         224,400          6.6        12.32      1.89
SS2         250,800         10.6        12.43      2.36
SS4          34,320          6.6        10.44      1.89
SS5          22,440          6.6        10.02      1.89

k = 2
n^ = 4  n2 = 4
N = 8

SSB = (T12/n1 + T22/n2) - T2/N
    = (2043.94/4 + 64.48/4) - 2834.5/8
    = (510.99 +16.12) - 354.31
    = 527.11 - 354.31
    = 172.80

MSB = SSB/k-1 = 172.80/1 = 172.80

SSW = E E Xji2 - 527.11
    = 531.97 - 527.11
    = 4.86

MSW = SSW/N-k = 4.86/6 =0.81

F = MSB/MSW = 172.80/0.81 = 213.3

Fk-l N-k = Fl 6 = 5«" (critical value for 95% confidence)
                          Appendix B - 3                    Rev.  3
-------
2) Nitrobenzene
          Treatment 1    Treatment 2       _      — -—
SSI         2.00X106          2610      14.51      7.87
SS2         2.44X106          2610      14.71      7.87
SS4         1.74X106          1305      14.37      7.17
SS5         1.74X106          2610      14.37      7.87

k = 2
nl = 4  n2 = 4
N = 8

SSB = (T12/n1 + T22/n2) - T2/N
    = (3359.36/4 + 947.41/4) - 7874.79/8
    = (839.84 + 236.85) - 984.35
    = 1076.69 - 984.35
    = 92.34

MSB = SSB/k-1 = 92.34/1 = 92.34

SSW = E E X£ -j2 - 1076.69
    = 1077. l4 - 1076.69
    = .45

MSW = SSW/N-k = 0.45/6 =0.08

F = MSB/MSW = 92.34/0.08 = 1154.25

Fk-l,N-k = Fl,6 = 5.99 (critical value for 95% confidence)
                          Appendix B - 4                   Rev.  3
-------
3) Cyanide


          Treatment 1    Treatment 2     x^         XT
SSI          6.06           6.63         1.80       1.89
SS2          4.80           5.38         1.57       1.68
SS4          3.53           2.89         1.26       1.06
SS5          3.16           2.36         1.15       0.86

k = 2
HI = 4  ri2 = 4
N = 8

SSB = (T12/n1 + T22/n2) - T2/N
    = (33.41/4 + 30.14/4) - 127.01/8
    = (8.35 + 7.54) - 15.88
    = 15.89 - 15.88
    = 0.01

MSB = SSB/k-1 = 0.01/1 =0.01

SSW = E E Xji2 - 15.89
    = 16.87 - 15.89
    = 0.98

MSW = SSW/N-k = 0.98/6 =0.16

F = MSB/MSW = 0.01/0.16 =0.06

Fk-l N-k ~ Fl 6 = 5-99 (critical value  for 95%  confidence)
                          Appendix B - 5                    Rev.  3
-------
                  Computational  Table for the F Value
Constituent
Benzene
Nitrobenzene
Total Cyanides
Source
Between
Within
Between
Within
Between
Within
Sum of
Squares
172.80
4.86
92.34
0.45
0.01
0.98
Degrees of
Freedom
1
6
1
6
1
6
Mean
Square
172.80
0.81
92.34
0.08
0.01
0.16
F
213.3*
1154.25*
0.06
* - Indicates that the calculated F value exceeds the critical value.
  Conclusion

  L/L Extraction followed  by steam stripping is more  efficient at
  reducing  the  concentration  of  benzene   and   nitrobenzene  in
  K103/K104 than L/L extraction alone,  but is not  more efficient at
  reducing the  concentration of total  cyanides in K103/K104  than
  L/L extraction alone.
                           Appendix B  -  6
Rev. 3
-------
ANOVA #2

Comparison of L/L Extraction Followed by Steam Stripping with L/L
Extraction  Followed  by Steam  Stripping  Followed by  Activated
Carbon Adsorption

Compare  sample  point SD-8  (Untreated Waste to  Activated Carbon
Adsorption  Beds)  with  sample  point  SD-9  (Treated  Waste  from
Carbon Adsorption System)

Regulated Constituents:   Benzene
                         Nitrobenzene
                         2,4-Dinitrophenol
                         Phenol
                         Aniline
                         Cyanide

Regulated Constituents Present in Untreated Waste  (SD-8):

                         Benzene
                         Aniline
                         2,4-Dinitrophenol
                         Phenol
                         Cyanide

Regulated Constituents Present in Treated Waste  (SD-9):

                         Benzene
                         Aniline
                         2 f4-Dinitrophenol
                         Phenol
                         Cyanide
                         Appendix  B  -  7                    Rev. 3
-------
1) Benzene (ug/1)
    AF = 1.32
Raw   SD-8
Corr. SD-8

Raw   SD-9
Corr. SD-9
  880
1161.60

  42
 55.44
2) Aniline (ug/1)
    AF = 1.10
Raw   SD-8
Corr. SD-8

Raw   SD-9
Corr. SD-9
 57000
 62700

  (30)
   33
  130
171.60

  (5)
  6.6
   ND
   ND

  (30)
   33
3) 2,4-Dinitrophenol (ug/1)
     AF = 1.25
  39
51.48

  19
25.08
56000
61600

 (30)
  33
  20
26.40

  11
14.52
300000
330000

 960
 1056
Raw   SD-8
Corr. SD-8
 53000
 66250
   ND
   ND
24000
30000
24000
30000
Raw   SD-9     380
Corr. SD-9     475
              320
              400
           260
           325
           230
           288
          Numbers  in  parentheses indicate that  the compound was
          not detected  in this sample.   The detection limit has
          been  used  in  place  of  the  actual  value for  this
          compound.   "ND" indicates  that this  compound  was not
          detected in the untreated waste (SD-8),  and hence this
          reading was not used in the ANOVA calculations.
                          Appendix B - 8
                                              Rev. 3
-------
4) Phenol (ug/1)
     AF = 4.76
Raw   SD-8     ND         29000    39000     41000
Corr. SD-8     ND         138040   185640    195160
Raw   SD-9    (30)         (30)    (30)       150
Corr. SD-9    142.8        142.8   142.8      714
5) Cyanide (mg/1)
     AF = 1.39
Raw   SD-8     6.850      4.590    3.470     0.952
Corr. SD-8     9.52       6.38     4.82      1.32
Raw   SD-9    0.565        0.597   0.156     0.129
Corr. SD-9    0.79         0.83    0.22      0.18
Note:     Numbers  in  parentheses indicate that  the compound was
          not detected  in this sample.   The detection limit has
          been  used  in  place  of  the  actual   value for  this
          compound.   "ND" indicates  that this  compound  was not
          detected in the untreated waste (SD-8), and hence this
          reading was not used in the ANOVA calculations.

(Above raw values  are taken  from the EPA's Onsite Engineering
Report for K103 and K104. Tables 6-13 and 6-14).
                          Appendix B - 9                    Rev. 3
-------
1) Benzene

          Treatment 1    Treatment 2      x^
SSI          1161.6         55.4         7.06      4.01
SS2           171.6          6.6         5.15      1.89
SS4            51.5         25.1         3.94      3.22
SS5            26.4         14.5         3.27      2.67

k = 2
nl = 4  n2 = 4
N = 8

SSB = (T^/ni + T22/n2) - T2/N
    = (377.14/4 + 139.00/4) - 974.06/8
    = (94.29 + 34.75) - 121.76
    = 129.04 - 121.76
    = 7.28

MSB = SSB/k-1 = 7.28/1 =7.28

SSW = E E Xi -j2 - 129.04
    = 139.73 - 129.04
    = 10.69

MSW = SSW/N-k = 10.69/6 =1.78

F = MSB/MSW = 7.28/1.78 =4.09

Fk-l N-k = Fl 6 = 5«" (critical value for 95% confidence)
                         Appendix B  -  10                    Rev.  3
-------
2) Aniline
          Treatment 1    Treatment 2
SSI          62700           33          11.05     3.50
SS2            ND            33            ND      3.50
SS4          61600           33          11.03     3.50
SS5         330000          1056         12.71     6.96

k = 2
HI = 3  n2 = 4
N = 7

SSB = (T12/n1 + T22/n2) - T2/N
    = (1210.34/3 + 304.85/4) - 2730.06/7
    = (403.45 + 76.21) - 390.01
    = 479.66 - 390.01
    = 89.65

MSB = SSB/k-1 = 89.65/1 = 89.65

SSW = E E Xji2 - 479.66
    = 490.49- 479.66
    = 10.83

MSW = SSW/N-k = 10.83/5 =2.17

F = MSB/MSW = 89.65/2.17 = 41.31

Fk-l N-k = Fl 5 = 6.61 (critical value for 95% confidence)
                         Appendix B - 11                   Rev.  3
-------
3)  2,4-Dinitrophenol

          Treatment 1    Treatment 2     	xi_      X2
SSI          66250           475         11.10     6.16
SS2            ND            400           ND      5.99
SS4          30000           325         10.31     5.78
SS5          30000           288         10.31     5.66

k = 2
HI = 3  n2 = 4
N = 7

SSB = (T^/ni + T22/n2) - T2/N
    = (1006.16/3 + 556.49/4) - 3059.20/7
    = (335.39 + 139.12) - 437.03
    = 474.51 - 437.03
    = 37.48

MSB = SSB/k-1 = 37.48/1 = 37.48

SSW = E E Xji2 - 474.51
    = 475.07 - 474.51
    = 0.56

MSW = SSW/N-k = 0.56/5 =0.11

F = MSB/MSW = 37.48/0.11 = 340.73

Fk-l N-k = Fl 5 = 6-61 (critical value for 95% confidence)
                         Appendix B - 12                   Rev.  3
-------
4) Phenol
          Treatment 1    Treatment 2
SSI            ND           142.8          ND       4.96
SS2          138040         142.8         11.84      4.96
SS4          185640         142.8         12.13      4.96
SS5          195160         714.0         12.18      6.57

k = 2
nl = 3  n2 = 4
N = 7

SSB = (Ti2/"! + T22/n2) ~ T2/N
    = (1306.82/3 + 460.10/4) - 3317.76/7
    = (435.61 + 115.02) - 473.97
    = 550.63 - 473.97
    = 76.66

MSB = SSB/k-1 = 76.66/1 = 76.66

SSW = t E Xi -j2 - 550.63
    = 552.64- 550.63
    = 2.01

MSW = SSW/N-k = 2.01/5 =0.40

F = MSB/MSW = 76.66/0.40 =  191.65

Fk-l N-k = Fl 5 = 6-6l (critical value  for 95%  confidence)
                         Appendix B - 13                    Rev.  3
-------
5)  Cyanide
          Treatment 1    Treatment 2
SSI          9.52            0.79        2.25      -0.24
SS2          6.38            0.83        1.85      -0.19
SS4          4.82            0.22        1.57      -1.51
SS5          1.32            0.18        0.28      -1.71

k = 2
n^ = 4  r\2 = 4
N = 8

SSB = (TiVni + T22/n2) - T2/N
    = (35.4/4 + 13.3/4) - 5.29/8
    = (8.85 + 3.33) - 0.66
    = 12.18 - 0.66
    = 11.52

MSB = SSB/k-1 = 11.52/1 = 11.52

SSW = E E Xji2 - 12.18
    = 16.33 - 12.18
    = 4.15

MSW = SSW/N-k = 4.15/6 =0.69

F = MSB/MSW = 11.52/0.69 =  16.70

Fk-l N-k = Fl 6 = 5-99  (critical value  for  95%  confidence)
                          Appendix B - 14                   Rev. 3
-------
                  Computational Table for the F Value
Constituent
Benzene
Aniline
2, 4-Dinitro-
phenol
Phenol
Total Cyanides
Source
Between
Within
Between
Within
Between
Within
Between
Within
Between
Within
Sum of
Squares
7.28
10.69
89.65
10.83
37.48
0.56
76.66
2.01
11.52
4.15
Degrees of
Freedom
1
6
1
5
1
5
1
5
1
6
Mean
Square
7.28
1.78
89.65
2.17
37.48
0.11
76.66
0.40
11.52
0.69
F
4.09
41.31*
340.73*
191.65*
16.70*
* - Indicates that the calculated F value exceeds the critical value.
  Conclusion

  L/L extraction followed  by steam stripping and  activated carbon
  adsorption is  more efficient  at reducing  the  concentration  of
  aniline,  2,4-dinitrophenol, phenol and cyanide in K103/K104 than
  L/L extraction followed by steam stripping alone, but is not more
  efficient at reducing  the concentration  of benzene  in K103/K104
  than L/L extraction followed by steam stripping alone.
                           Appendix B - 15
Rev. 3
-------










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------- APPENDIX 0 Calculation of Treatment Standards Constituent: Benzene Effluent 1 Sample Set Concentration (mg/l) 1 0.042 2 0.005 4 0.019 5 0.011 1 Percent 2 Recovery 76 76 76 76 Accuracy 3 Correction Factor 1.32 1.32 1.32 1.32 x = Corrected Concentration (tng/l) 0.055 0.007 0.025 0.015 0.026 4 Log 5 Transform -2.900 -4.962 -3.689 -4.200 y = -3.938 s = 0.867 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-12. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-3.938 + 2.33(0.867)) = exp (-1.918) = 0.147 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 01147 / 0.026 = 5.654 Treatment Standard = Corrected Effluent Mean X VF = 0.026 X 5.654 = 0.147 mg/l Appendix D - 1
------- APPENDIX D Calculation of Treatment Standards Constituent: Aniline Effluent 1 Sample Set Concentration (mg/l) 1 0.030 2 0.030 4 0.030 5 0.960 I Percent 2 Recovery 91 91 91 91 Accuracy 3 Correction Factor 1.10 1.10 1.10 1.10 X Corrected 4 Concentration (mg/l) 0.033 0.033 0.033 1.056 0.289 y s Log 5 Transform -3.411 -3.411 -3.411 0.054 = -2.545 = 1.733 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, tn, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y +• 2.33s) where y = the mean of the tog transforms s = the standard deviation of the log transforms. Therefore, C = exp (-2.545 + 2.33(1.733)) = exp (1.493) = 4.450 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF - C / x = 4.450 / 0.289 = 15.398 Treatment Standard = Corrected Effluent Mean X VF = 0.289 X 15.398 = 4.450 mg/l Appendix D - 2
------- APPENDIX D Calculation of Treatment Standards Constituent: 2,4-Dinitrophenol Sample Set 1 2 4 5 Effluent 1 Concentration (ing/ 1) 0.380 0.320 0.260 0.230 Percent Recovery 80 80 80 80 Accuracy 3 2* Correction Factor 1.25 1.25 1.25 1.25 Corrected 4 Concentration (mg/l) 0.475 0.400 0.325 0.288 Log 5 Transform -0.744 -0.916 -1.124 -1.245 X = 0.372 y = -1.007 s = 0.222 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. * - Average of Percent Recovery for Semivolatiles with greater than or equal to 20% recovery as listed in Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the tog transforms. Therefore, C = exp (-1.007 + 2.33(0.222)) = exp (-0.490) = 0.613 and VF = C / x . 99 where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 0.613 / 0.372 = 1.648 Treatment Standard = Corrected Effluent Mean X VF = 0.372 X 1.648 = 0.613 mg/l Appendix D - 3
------- APPENDIX D Calculation of Treatment Standards Constituent: Nitrobenzene Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.03 0.03 0.03 0.03 115 115 115 115 0.87 0.87 0.87 0.87 0.026 0.026 0.026 0.026 -3.650 -3.650 -3.650 -3.650 0.026 y = s = -3.650 0.000 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): C = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-3.650 + 2.33(0)) = exp (-3.650) = 0.026 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 0?026 / 0.026 = 1 A variability factor of one was not used in calculating the treatment standards. The variability factor of 2.80 was substituted for the value 1. VF = 2.80 Treatment Standard = Corrected Effluent Mean X VF = 0.026 X 2.80 = 0.073 mg/l Appendix D - 4
------- APPENDIX D Calculation of Treatment Standards Constituent: Phenol Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.030 0.030 0.030 0.150 21 21 21 21 4.76 4.76 4.76 4.76 0.143 0.143 0.143 0.714 -1.945 -1.945 -1.945 -0.337 0.286 y = s = -1.543 0.804 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-13. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm. In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): coo = exp (y + 2-33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-1.543 + 2.33(0.804)) = exp (0.330) = 1.391 and VF = C / x where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 1?391 / 0.286 = 4.864 Treatment Standard = Corrected Effluent Mean X VF = 0.286 X 4.864 = 1.391 mg/l Appendix D - 5
------- APPENDIX D Calculation of Treatment Standards Constituent: Total Cyanides Sample Set Effluent 1 Concentration (mg/l) Percent 2 Recovery Accuracy 3 Correction Factor Corrected 4 Concentration (mg/l) Log 5 Transform 0.565 0.597 0.156 0.129 72 72 72 72 1.39 1.39 1.39 1.39 0.785 0.830 0.217 0.179 -0.242 -0.186 -1.528 -1.720 0.503 y = s = -0.919 0.818 1 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 6-14. 2 - Obtained from the Onsite Engineering Report, E. I. du Pont de Nemours, Table 7-14. 3 - Accuracy Correction Factor = 100 / Percent Recovery. 4 - Corrected Concentration = Effluent Concentration X Accuracy Correction Factor. 5 - Log Transform using the natural logarithm, In, of the Corrected Concentration. Treatment Standard = Corrected Effluent Mean X VF Calculation of Variability Factor (VF): GO, = exp (y + 2.33s) where y = the mean of the log transforms s = the standard deviation of the log transforms. Therefore, C = exp (-0.919 + 2.33(0.818)) = exp (0.987) = 2.683 and VF = C / x 99 where x = the mean of the corrected effluent concentrations. Therefore, VF = C / x = 2?683 / 0.503 = 5.334 Treatment Standard = Corrected Effluent Mean X VF = 0.503 X 5.334 = 2.683 mg/l Appendix D - 6
------- APPENDIX E - ANALYTICAL QA/QC The analytical methods used for analysis of the regulated constituents identified in Section 5 are listed in Table E-l. SW-846 methods (EPA's Test Methods for Evaluating Solid Waste; Physical/Chemical Methods. SW-846. Third Edition, November 1986) are used in most cases for determining total waste concentrations. Deviations from SW-846 methods required to analyze the sample matrix are listed in Table E-2. These deviations are approved methods for determining constituent concentrations. SW-846 also allows for the use of alternative or equivalent procedures or equipment; these are described in Tables E-3 through E-5. These alternatives or equivalents included use of alternative sample preparation methods and/or use of different extraction techniques to reduce sample matrix interferences. The accuracy determination for a constituent is based on the matrix spike recovery values. Table E-6 present the matrix spike recovery values for total waste concentrations of benzene, aniline, nitrobenzene, and phenol for K103/K104 and for total cyanides for K104 for the EPA-collected data. Because 2,4-dinitrophenol matrix spike recoveries were not collected, the V- average of the percent recoveries equal to or greater than 20% for all semivolatiles was used as the percent recovery for 2,4-dinitrophenol. Appendix E-l
------- The accuracy correction factors for the regulated constituents for the treatment residuals are presented in Table E-6. The accuracy correction factors were determined in accordance with the general methodology presented in the Introduction. For example, for benzene, actual spike recovery data were obtained for analysis of liquid matrices and the lowest percent recovery value was used to calculate the accuracy correction factor. An example of the calculation of the corrected concentration value for benzene is shown below. Analytical Correction Corrected Value % Recovery Factor Value 0.042 mg/1 76 100 = 1.32 1.32 X 0.042 = 0.055 mg/1 76 Appendix E - 2
------- Table E-1 Analytical Methods for Regulated Constituents Regulated Constituent Analytical Method Method Number Volatiles Benzene Purge and Trap 5030 Gas Chromatography/Mass 8240 Spectrometry for Volatile Organics Semivolatiles AniIine 2,4-Dinitrophenol Nitrobenzene Phenol Continuous Liquid/Liquid 3520 Extraction Gas Chromatography/Mass 8270 Spectrometry Column Technique Inorganics Cyanides Total and Amenable Cyanides 9012 a - Environmental Protection Agency. 1986. Test Methods for Evaluating Solid Waste. Third Edition. U. S. EPA. Office of Solid Waste and Emergency Response. November 1986. Appendix E - 3
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------- Table E-5 Specific Procedures or Equipment Used for Analysis of Cyanides When Alternatives or Equivalents are Allowed in the SW-846 Methods8 Analysis SU-846 Sample Alternatives or Equivalent Method Aliquot Allowed by SW-846 Methods Specific Procedures Used Total and amenable cyanide 9012 500 ml Hydrogen sulfide treatment may be required. Hydrogen sulfide treatment was not required. A Fisher-Mulligan absorber or equivalent should be used. A Vheaton Distilling Apparatus absorber was used. a - Onsite Engineering Report of Treatment Technology Performance for E. I. duPont de Nemours, Inc., Beaumont, Texas. Table 7-6. Appendix E - 10
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------- The comparative method of measuring thermal conductivity has been proposed as an ASTM test method under the name "Guarded, Comparative, Longitudinal Heat Flow Technique". A thermal heat flow circuit is used which is the analog of an electrical circuit with resistances in series. A reference material is chosen to have a thermal conductivity close to that estimated for the sample. Reference standards (also known as heat meters) having the same cross-sectional dimensions as the sample are placed above and below the sample. An upper heater, a lower heater, and a heat sink are added to the "stack" to complete the heat flow circuit. See Figure 1. Appendix F - 1
------- GUARD GRADIENT STACK GRADIENT" THERMOCOUPLE BOTTOM REFERENCE SAMPLE LOWER; STACK HEAER LIQUID HEAT COOLED SINK HEAT FLOW DIRECTION •v — ' UPPER GUARD HEATER / K A/ \ / K LOWER GUARD HEATER FIGURE 1 SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD Appendix F - 2
------- The temperature gradients (analogous to potential differences) along the stack are measured with type K (chromel/alumel) thermocouples placed at known separations. The thermocouples are placed into holes or grooves in the references and also in the sample whenever the sample is thick enough to accommodate them. For molten samples, pastes, greases, and other materials that must be contained, the material is placed into a cell consisting of a top and bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2 inch in diameter and .5 inch thick. Thermocouples are not placed into the sample but rather the temperatures measured in the Pyrex are extrapolated to give the temperature at the top and bottom surfaces of the sample material. The Pyrex disks also serve as the thermal conductivity reference material. The stack is clamped with a reproducible load to insure intimate contact between the components. In order to produce a linear flow of heat down the stack and reduce the amount of heat that flows radially, a guard tube is placed around the stack and the intervening space is filled with insulating grains or powder. The temperature gradient in the guard is matched to that in the stack to further reduce radial heat flow. The comparative method is a steady state method of *• measuring thermal conductivity. When equilibrium is reached the heat flux (analogous to current flow) down the stack can be determined from the references. The heat into the sample is given by Appendix F - 3 January 1988
------- - xtop(dT/dx)top and the heat out of the sample is given by where bottom X = thermal conductivity dT/dx = temperature gradient and top refers to the upper reference while bottom refers to the lower reference. If the heat was confined to flow just down the stack, then Q^n and Qout would be equal. If Q^n and Qout are in reasonable agreement, the average heat flow is calculated from - Win + Qout>/2' The sample thermal conductivity is then found from Appendix F - 4 tnnn * January 1988
------- ^sample " Q/(dT/dx)sample The result for the K102 Activated Charcoal Waste tested here is given in Table 1. The sample was held at an average temperature of 42C with a 53C temperature drop across the sample for approximately 20 hours before the temperature profile became steady and the conductivity measured. At the conclusion of the test it appeared that some "drying" of the sample had occurred. Appendix F - 5
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