Free Reply to Response to Motion - District Court of Federal Claims - federal

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Exhibit 18

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April 19, 1991

Mr. Todd S. Parkhurst Schiff Hardin & Waite 7200 Sears Towei" Chicago, IL 60606-6473 RE: Patent Application: MAECTITETM Treatment Process

Dear Mr. Parkhurst:

I am pleased to file this completely revised patent application with your office for your review and processing it further.
Since last application dated March 16, 1990, USEPA regulations have changed with respect to the definition of lead-toxic wastes, we had no choice but to prepare a new application. The EP toxicity test has been replaced with toxicity characteristic leaching procedure (TCLP) which is much more rigorous than the former in extracting the leachable lead from solid wastes and contaminated soils. I am attaching a copy of regulatory issues on Land Disposal Prohibitions for your information. As you shall note ! have also changed the 'qitle" with better wording that fits the USEPA terminology. Although, this patent application presents the same innovative technology as earlier (Serial No. 494,774), but it covers in-depth the regulatory changes, additional examples to demonstrate that. the technology meets the new regulatory criteria on a wide variety of lead-toxic solid wastes, and a better schematic block diagram (Figure, 1) to meet the need of the Patent office. The application also documents that MAECTITETM Treatment Process is a novelty developed originally by the inventors for lead fixation in solid wastes. We at MAECORP deeply appreciate your patience, expert advice and appropriate action on filing the enclosed application with the Patent office under the same expedited schedule and clause as the previous application.

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Page 2 " Patent Application.

Please feel free to contact us should you require further information pertaining to this patent application.
I look forward to hearing from you in due course of time. ¯ Kind regards, MAECORP Incorporated

Dhiraj Pat, Ph.D. Director/Technical Support Group

Karl Yost Phil Newton Veto Diedrick Henry Mendoza

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FIXATION AND STABILIZATION OF LEAD IN CONTAMINATED SOIL AND SOLID WASTE ~I~D OF THE INVENTION The present invention be!ongs to the field of chemical treatment techno!ogy applicable to contaminated soils and solid waste materials containing unacceptable levels of leachable lead. More specifically, the invention disclosed herein pertains to a new lead fixation technology innovated and commercialized under the trademark, "MAECTITE~ Treatment Process" for lead toxic soils and hazardous solid waste materials that fall under the current landban regulations. This novel technology is directly applicable to management of lead-toxic hazardous solid wastes under D008 waste code assigned by the USEPA. BACKGROUND OF T~E INVENTION Lead as a contaminant is often found in the soils around lead smelters, and' battery breaking/recycling, facilities and foundries including metal and leaded gasoline manufacturing plants. This occurs when lead-containing chemicals are used in the plants, and wastewater containinq the lead is allowed to spill over or drain into the soil. Many abandoned hazardous waste sites are heavily contaminated with lead, threatening human health, the food chain, the ecosystem and the environment. National Contingency Plan (NCP) along with Superfund Act (CERCLA) and Superfund Amendments Reauthorization Act (SARA) specify the remediation of such sites as those containing lead-toxic soils and solid wastes. The Resource Conservation and Recovery Act of i976, commonly known as the RCRA, provided for federa! classification of hazardous waste. The statutory language defines '~hazardous waste" as soli4 waste or combinations of solid waste which pose a "substantial present or potential hazard...when improperly treated, stored, transported, or disposed of, or otherwise mismanaged". Any solid waste that. exhibits one of the hazard characteristics defined in Subpart C of Part 261, Volume 40, Code of Federal Regulations is, by definition, a hazardous waste. A solid waste is considered to be a hazardous ~waste if it exhibits characteristics of either ignitability, corrosivity~ DG0163

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reactivity, or toxicity characteristic leaching procedure (TCLP). Historically, toxicity characteristic regulations had been based on extraction procedure (EP) toxicity test (USEPA Method 1310). which specified laboratory steps to be followed in analyzing samp~es. The test wai aimed at identifying the tendency of wastes to generate a leachate with concentrations of contaminants greater than the values listed in Appendix II of the Code of Federal Regulations, Part 261.24, page 406, revised July i, 1988. If. concentrations of leachable, mobile lead were found to be greater than 5 milligrams per liter, the material was considered characteristically toxic for lead and hence hazardous with respect to lead content. Such characteristically toxic wastes required treatment to comply with the USEPA regulations defining the treatment standards for lead and other parameters of concern. This EP Toxicity test is now obsolete and has been replaced by toxicity characteristic leaching procedure (TCLP), USEPA Method 1311 for 39 different parameters including lead. Effective November 8, 1990, the treatment standard for lead wastes (D008), particularly lead contaminated soils and solid wastes, has been established at a toxicity characteristic level of 5 milligrams per liter in the extraction fluid by the TCLP (Toxicity Characteristic Leaching.Procedure) test ~USEPA Method 1311) with the latest revision published in 55FR26986-26998, dated June 29,~ 1990. The TCLP test is much more rigorous and uniformly applicable to a larger number of parameters than the EP toxicity test. The TCLP test replaces the EP toxicity method for RCRA waste determination. TCLP test requires sizing of waste materia! to less than 3/8 inches or 9.5 mm and agitation of 100g waste sample in 2 liter of specified extraction fluid for 18 hours on a rotating agitator at a speed of about 30 revolutions per minute. The lead concentration is determined in the extraction fluid after filtration under pressure and expressed in units of milligrams per liter (mg/l). Any solid waste that contains leachable lead levels in TCLP excess of 5 milligrams per liter is considered characteristically toxic and hence hazardous. Such hazardous waste must be treated with one or more Best Demonstrated Available Technology (BDAT) DG0164 T-X006 2

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and/or with an alternative technology to decharacterize the waste for lead toxicity; that is, decrease TCLP lead in extract to levels below 5 milligrams per liter in order to permit it for land disposal. Land disposal included waste staging on land surface; placing it in .a landfill; surface impoundment; waste piling; injection wells; land treatment facility (land farming); salt dome or salt bed formation; underground mlne or caving; and concrete vault or bunkering. Land disposal restrictions ban treated wastes with TCLP lead levels greater than 5 milligrams per liter in the leachate. Such characteristically lead toxic wastes must be treated with a cost effective and practical technoloqy that is commercially available and that provides substantial treatment including a decrease in risk to human health and the environment. Prior to the MAECTITE- Treatment Process (MTP) deve!opment and innovation for contaminated soils and solid wastes (D008), there existed no known patented and/or otherwise innovative technology that could be applied (i) cost effectively at the commercial scale to treat lead-toxic soils and solid wastes, (ii) to decrease the waste volume and at the same time work under substantially dry conditions with no generation of wastewater or other byproducts, (iii) to comply with the latest and final land ban regulations (55 FR22693-22694), (iv) to cure in few hours for rapid sampling and final internment evaluation and (v) to a wide variety of lead-toxic solid wastes, soils and sludges with a tremendous flexibility of scale and mobility. Various conventional methods have been tried to remove leachable, mobile lead from soils and solid waste materials. Those methods include washing, leaching and extracting the lead. According to conventional practice, contaminated soil or solid waste material is excavated from the ground for processing and/or washing. During washing, the contaminated materia! is immersed in water or other specified solutions while it is being agitated. Leaching involves the removal of lead from contaminated material by the use of water or liquid chemicals. Extraction is a form of leaching wherein water or liquid chemicals are used at elevated ~emper¯atures and increased pressure to remove the lead. DG0165
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None of the prior art processes reduces the TCLP lead content to below 5 milligrams of lead per liter in the extract from treated soil or solid wastematerial. Other methods for removing lead from contaminated soil or solid waste involve the use of water in the formation of slurries, which require cur~bersome equipment for the separation of lead from the waste material. The.separated solids are usually wet, that is, the end product fails the Paint Filter Test, (USEPA Method 9095). And therefore, further processing of wet materials is required before disposal as a stabilized material. The additional steps required in the treatment by conventional wet processing of contaminated soil and solid waste are So. costly as to become prohibitive. Other conventional techniques involve the chemical fixation of lead in contaminated soils and solid waste. One well-known technique according to the International Technical Information Institute (ITI) involves the extraction of lead using nitric acid and/or aqua regia, and a subsequent purging of the resultant lead nitrate solution with hydrogen sulfide gas to precipitate the lead nitrate as lead ¯sulfide. However, the use of noxious hydrogen sulfide gas necessitates specific health and safety measures which increase environmental remediation costs. ¯ Falk e__~t, a_!l. (1987) in U.S. Patent No. 4,687,373 describe a composition which encapsulates contaminants such as lea~ in soils, sludges, sediment and ash. A cementitious matrix in the¯ form of metal metasilicates is fo~med to encapsulate the contaminants; however, the metal metasilicates increase the volume and weight of the treated soil or solid waste material. Hemwell (U.S. Patent No. 3,201,268) describes a method for stabilizing clay soils by mixing phosphoric acid and sulfuric acid with the soil, which is then further mixed with a Water-soluble lead salt. The resulting composition may be compacted and cured to produce a stabilized mass strength as compared with untreated soil. This method is suitable for the stabilization of argillacepus soils and clays containing aggregates. Webster e_~t. a__~l. (1977) in U.S. Patent No. 4,028,130 describe a method for disposing and using municipal sewage plant waste

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materials, more particularly digestive sewage sludge. The sludge is treated with cementitious reactants, including calcium sulfate/ to form a hardened product for subsequent disposal. The sewage sludge
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contains heavy metals, such as lead, which may be involved in the cementitious reaction. Gouvenot (U.S. Patent No. 4,615,643) describes a method of sealing off a mass of stored waste in soil containing heavy metal cations. An additive is added to the sol! which comprises cement, clay, silicone, sodium carbonate and alkalimetal pyrophosphate. The lead cation forms water-insoluble compound upon reaction with the sodium carbonate and pyrophosphate. The process requires a long curing time and has limited commercial application. stanforth (U.S. Patent No. 4,889,640) teaches a method of fixation using reactive calcium carbonate, reactive magnesium carbonate, and reactive calcium magnesium carbonate for reaction with lead and cadmium in hazardous solid wastes (pH 6 to 9) from foundries and metal operations. Stanforth's technique reduces EPTOX lead and cadmium in hazardous wastes when treated with a wate~ softening lime sludge (a source for reactive carbonates of calcium and magnesium). Stanforth cited the work of Inglis (U~S. Patent No. 4,652,381) where crystalline and non-reactive forms of calcium carbonate (Such as limestone) are mixed with a highly acidic wastewater (pH 2) to pr~cipitate lead, copper and zinc out with formation of a sludge that might contain significant amounts of leachable metals. This solid waste sludge requires further treatment in order to render it non-hazardous prior to its disposal. Stanforth reported, "It has been found that limestone (calcium carbonate) is relatively inefficient at removing heavy metals such as lead 'and cadmium from hazardous solid or sludge waste such as that which is formed in foundries and other factories which process metal. The limestone doesn't react in solid waste at a high enough rate to release sufficient carbonates to react and combine with the heavy metals." Furthermore, it is common knowledge that carbonates decompose under acid conditions and liberate carbon dioxide as wel! as metals that may endanger the environment under such conditions as acid rain or landfill leachate. DG0't 6"7

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Bonee (Patent No. 4,701,219) discloses the treatment of spent sorbent waste waters (containing leachable Vanadium, Nickel, and Sodium) with alkaline earth metal compounds. He finds that powdered lime (calcium hydroxide or calcium oxide) and calcium fluoride were most effective in decreasing the leachable Vanadium and .Nickel. Bonee's data confirm that calcium carbonate, sodium hydroxide, and~ calcium sulfate, and ~sodium bicarbonate are not effective in preventing the leaching of Vanadium and nickel. Bonee measured nickel and sodium only when Vanadium was at least partially removed by treatment of waste with powdered lime or calcium fluoride. From this patent, it may be concluded .that use of calcium fluoride and/or~ powdered~lime would be more effective for Vanadium and nickel immobilization than the use of calcium carbonate and/or calcium sulfate. The chemistry of lead in soils is far different than that of Vanadium and Nickel in sorbent or spent catalyst wastes. Lead biogeochemistry and fate in the environment follow pathways similar, to that of calcium. Due to the Similarities in the chemistry of lead and calcium, the secondary smelters do not accept lead rich wastes that are high in calcium. Douglas et. a_!l. (Patent No. 4,671,882) taught an art of generating non-hazardous sludge from wastewaters containing a mixtureof metals. They added phosphoric acid to the wastewater to a pH of less than 5.0. ~hey. further treated it with a coagulant ferric chloride and raised the pH in the range of 7 to 8.5 with calcium hydroxide.~ Douglas eta! used an anionic polymer (DREW FLOC 270) as a flocculant to aid dewatering. The resulting sludge contained heavy metals in non-leachable form by EP Toxicity test criteria. The method deve!oped by Douglas et al for industrial wastewater treatment creates sludge that is characteristically nonhazardous by EP toxicity criteria for zinc, lead, chromium, nickel, copper and cadmium. Since EP toxicity criteria is now obsolete, a testing of this sludge for TCLP metals is warranted under the current land ban regulations. Their systematic methods generated supernatant, a wastewater stream, containing 1 ppm lead ~S compared to a standard limit of 0.05 ppm lead for drinking water under the Safe Drinking Water Act (SDWA). This necessitated further treatment

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of the supernatant during dewatering operations for removal of residual metals. The systematic methodology deve!oped by Douglas e_~t a_!l is very broad in scope for treatment of hazardous wastewaters associated with generation of a non-EP Toxic Sludge and a supernatant wastewater with residual metals. The method is not transferable to lead contaminated soils and solid wastes at any scale. An innovative and cost-efficient technology is needed that does not generate wastewater or supernatant and that treats the lead-toxic soils and D008 solid wastes under relatively dry conditions and fixates the leachable lead to levels below 5 milligrams per liter by TCLP test criteria as required under EPA regulations. Experimental results from MAECTITE- Treatment Process (MTP) show that phosphoric acid alone fails to pass the TCLP lead criteria for lead contaminated soils, and addition of lime (calcium oxide), to phosphoric acid treated soils further increases the TCLP lead levels. Stabilization of lead in soils and solid waste is crucial and a Best Demonstrated Available Technology (BDAT) is urgently needed, that must be (a) relatixely simple and feasible treatment techno!ogy for hazardous solid wastes; (b) commercially demonstrated and practical, (c) economically applicable and transferable to different lead contaminated sites, (d) rapid, and (e) generates no side streams or bypro4uct' wastes. The MAECTITE- Treatment technology as described in this patent application meets all these criteria of BDAT. The conventional processes, typically, do not reduce levels of leachable lead below the maximum concentration of contaminant allowed under current land ban regulations as per TCLP lead tests. Moreover, some of the conventional methods involve wet processing that is burdensome, cost prohibitive, and requires a considerable amount of equipment to separate the lead from the contaminated soil or solid waste material. Other methods based on cementation technology require~at least 28 days of curing time, increase the waste volume, and may raise, the

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pH in the range of 12.5 to 13.5.

Hardened concrete materia! is not DG0169

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conducive to retreatment in the event treatment fails TCLP confirmatory testing; The methods utilizing lime kiln dust, calcium carbonate and/or powdered lime for lead fixation are temporary solutions for lead treatment. Furthermore, these methods increase
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the waste volume and mass, and therefore, dilute the lead in the final waste matrix. Accordingly, there existed an urgent need for a commercially viable and proven techno!ogy for treatment of lead-toxic soiid wastes and soils. MAECTITE~ treatment technology has been invented, developed, and applied on a full scale to immobilize .leachable lead in contaminated soils and Solid waste materials economically. The~ innoQative treatment technology disclosed here brings the level of leachable lead in solid wastes, after treatment, to that below the TCLP limit required by the regulatory agencies. The novelties of the MAEC~ITE- Treatment technology are that it produces a stabilized treatment material suitable for disposal in compliance with the land ban regulations and it decreases the overal! waste volume to minimize transportation and internment costs. The MAECTITE- treatment technology works under relatively dry conditions to provide for easy handling of solid materials; it generates ~no wastewater or other byproducts and is relatively inexpensive as well as simple inall processing steps. SUMMARY ~OF THE INVENTION The present invention re~ates to a chemical treatment technology, commercially marketed under ~the tradename "MAECT!TETreatment Process", that immobilizes leachable lead in contaminited soils and solid waste miterials in two steps: Step One (I) of the process comprises contacting lead in the contaminated soil or~ the solid waste materia! with a gypsum powder, calcium sulfate dihydrate, that is mixed uniformly and thoroughly to dry-coat o~ cover the waste particles and aggregate as homogeneously as technically practical. This step conditions the solid waste matrix for the next step. The

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limited solubility, and direct physical contact of gypsum powder leads to a chemical reaction that converts a portion of the leachable lead into hard sulfates known as anglesites and calcium substituted anglesites which are substantially insoluble in water. Step Two (II) of the MAECTITE- Treatment Process comprises contacting the remaining leachable lead in the gypsum amended solid waste material with a phosphate supplying reagent, particularly phosphoric acid in concentrations ranging from 2% to 75% in water. This intimate contact requires intricate physical mixing in a pugmill to induce a series of chemical reaCtiOns that convert most or all of the leachable lead into water-insoluble forms such as hydroxy lead apatites, calcium substituted pyromorphites and mixed sulfate-phosphate minerals during the curing period. During this step, all or most of the carbonates and bicarbonates are decomposed in stoichiometric amounts by the phosphoric acid. As a result, acid sensitive ceru.ssites are destroyed and new acid resistant mineral species are formed. Approximately four (4) hours of curing time is required after a thorough mixing of the gypsum powder and phosphoric acid with the solid wastes and contaminated soils. Longer than 4 hours is preferable particularly when the moisture content of the soil is either too low or too high. The optimum reactions proceed at moisture content ranging from about i0 percent to about 40 percent by weight of the treated mixture. Under moist and wet conditions, additional time may be required for drying in a well-ventilated building or area constructed to protect the treated material from rain and harsh Weather conditions. It may take 2 to 5 days for the appropriate drying inside a well-ventilated building. Drying decreases both the treated mass and waste volume.. One of.the most unique feature and novelty of the MAECTITE~ Treatment Process is that it generates no wastewater. The second novelty and most important feature of the MAECTITE- Treatment Process is that the waste material undergoes a volume reduction DG0171 T-X006 9

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depehding on the initial characteristics and composition. The third novelty and important feature is that the lead-fixation is permanent and irreversible under natural environment. The TCLP lead valuesas well as EPTOX lead values continue to drop with time. During Step¯ One (I) of the MAECTITE- Treatment Process, the calcium sulfate converts the leachable lead to a hard sulfate mineral salt of the barite family, such as anglesite and calciumsubstituted anglesite or mixed calcium anglesite of nominal formula, PbSO4, Ca0.05.Pb0.95S04, Ca0.2Pb0.sS04, and Ca0.3Pb0.7S04. The phosphate supplying reagent is preferably phosphoric acid dissol~ed in water in amounts rgnging from about 2 per cent to about 75 per cent by weight. Phosphate ions. react with the remainder of the leachable lead and lead to the synthesis of superhard mixed minerals of the apatite family, such as r~ck phosphates or calcium substituted hydroxy lead apatite, lead hydroxy/chlor apatites, and pyromorphites With various degrees of substitution by calcium and sulfate ions. Presence of both excess sulfate and phosphate.together results in formation of insoluble "hard" and "superhard" mixed minerals of lead, such as calcium lead phosphate with the typical chemical. forr~ula, Ca0.05Pb0.95(P04)0.5 (S04)0.25 and Ca0.2Pb0.8(SO4)0.76(P04)0.16. Trace amounts of organo-lead phosphate sulfate are also formed. .All these minerals of lead are heavy, with densities greater thai 5.0, and resistant to dissolution in weak acids and/or water. The presence of excess Ca++ P04-3 SO4-2 and H30+ is essential for the geochemical reactions to proceed and complete for effective binding, fixation and stabilization of leachable lead as measured by TCLP test criteria. The combined use of both gypsum powder and the phosphoric acid produces the best and most acceptable results in decreising the leachable lead content of the contaminated soils and solid wastes chemically This treatment technology stabilizes lead in soils and

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solid wastes under ambient temperature (preferably > 30 F), pressure and humidity with no generation of a byproduct wastewater. The treated waste material is within the established treatment standard set .for non-hazardous waste. Current land disposal restrictions for lead-toxic wastes (D008) by the USEPA (55 FR 22520) require the development and application of the Best Demonstrated Available Technology (BDAT). MAECTITE- treatment technology satisfies all the requirements of the BDAT (Best Demonstrated Available Technology). BRIEF DESCRIPTION OF THE DRAWINGS .In the drawing, which comprises a portion of this disclosure: Figure 1 is a.block diagram of one embodiment of the treatment technology of the present .invention currently being commercialized under the trademark, "MAECTITE- Treatment Process." DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT The .treatment technology according ~to the present invention consists of a two-step process for treating contaminated soils and/or solid waste materials with chemical treating agents that convert leachable . lead to synthetic (man-made) substantially insoluble lead mineral crystals. As used herein, "substantially insoluble'" means the leachable lead content in the treated.waste sample is less than 5.0 milligrams per liter in the extract by the TCLP test (USEPA Method 1311). The first step of this novel process comprises the reaction of leachable lead in contaminated soils or solid waste materials with a gypsum powder, chemically known as calcium Sulfate dihydrate or CaSO4.2H20. Calcium sulfate dihydrate powder reacts with leachable and mobile lead species in wastes and forms "hard sulfates", which are relatively insoluble in water. In this invention, the powder form of dry calcium sulfate dihydrate or gypsum is preferred for blending with lead contaminated materials because it provides a uniform cover or dry coating over the surfaces of the waste particles and agggegates under low moisture conditions. It is preferred for most benefit and fast reaction that 95% of~the powder pass a i00 mesh sieve and remaining 5% must pass a 20 mesh sieve, However, sulfuric acid and alum in liquid or powder form can also be

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