Free Motion for Summary Judgment - District Court of Federal Claims - federal

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Exhibit 12

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US005202033A

United States Patent
Stanforth et al.

[19]

In] Patent Number: 5,202,033 [45] Date of Patent: Apr. 13, 1993
5,0371479 8/1991 Stmfforth ............................ 106/691 5,061,119 10/1991 Balthaus et al ..................... 210/747 OTI-I~R PUBLICATIONS Nagle, D. L., R. R. Stanforth, P. E. Durancean and T. P. Kunes, 1983, "AFS Transactions, Treatment of Hazardous Foundry Melting Furnace Dust and Sludges," vol. 91, pp. 715-720. Turpin, P. D., T. R..Stalzenburg, W. A. Stephensl and T. P. Ktme~, 1985, "AFS Transactions, Methods to Treat EP Toxic Foundry Waste~ and Waste Waters," vol. 93, pp. 737-740. Pn'mary'Examiner--Stan~ey S. Sflverman Assistant Examiner~Neil M. McCarthy Attorney, Agent, or Firm--Lathrop & Clark

IN SITU METHOD FOR DECREASING HEAVY METAL LEACHING FROM soILoR WASTE [75] Inventors: Robert R. Stanforth; Ajit K. Chowdhury, both of Madison, Wis. [73] Assignee: RMT, Inc., Madison, Wis. [21] AppL No.: 767,$20 [22] Filed: Sep. ~0, 1991 [51] Int. CI.5 .......................... C~2E 11/14; B09B 3/00 [52].. U.S. CI ..................................... 210/747; 210/751; 210/912; 210/911; 405/128; 405/129; 405/263; 588/236; 588/256 [58] Field of Search ............... 210/747, 751, 912, 911; 405/128, 129, 263; 588/231, 236, 253, 256; 423/34, 35, 42, 55, 57, 87, DIG. 20 References Cited [56] U.S. PATENT DOCUMENTS 3,094,846 6/1963 Peeler, Jr ............................ 210/747 3,962,080 6/1976 Dulin et al ............................ 210/59 4,268, ! 88 5/1981 Bertus et a] ......................... 405/128 4,354,942 10/1982 Kalzur et al ........................ 210/747 4,547,290 10/1985 Piehat .................................. 210/751 4,582,611 4/1986 Wang .................................. 210/747 4,671,882 6/1987 Douglas et al ...................... 210/720 4,687,373 8/1987 Falk et al ............................ 405/128 4,737,356 5/1988 O'Hara et al ..............: ........ 423/659 4,761,182 8/1988 Whitesearver et al ............... 106/98 4,781,841 11/1988 Sameya ............................... 210/747 4,861,482 8/1989 Frankenberger, Jr. et a/ .... 210/747 4,878,944 11/1989 Rolle et al .............................. 75/25 4,889,640 12/1989 Stanforth ............................ 210/751 4,927,293 5/1990 Campbell ............................ 405/128 4,948,516 8/1990 Fisher et al ......................... 210/751 4,950,409 8/1990 Stanforth ............................ 210/751 4,981,393 1/1991 van de Velde et al ............. 405/128 ¯ 4,988,376 1/1991 Mason ct al .......................... 65/134 5,013,185 5/1991 Takl ..................................... 405/128 5,024,556 6/1991 Tim.merman ........................ 405/128 5,028,272 7/1991 Bonee .................................. 106/792 5,037,240 8/1991 Sherman ............................. 405/128.

157]
A method of treating solid waste in soil or solid disposed waste containing unacceptable levels ofl~aehable metals, such as lead, eadmiuml arsenic, zlne, copper and chromium, inelude~ mixing the solid waste or soft in place with a phosphate source or a carbonate source or ferrous sulfate. After the solid waste and the additive are mixed, if needed an additional pH controlling agent is mixed into the soil or waste and additive. After the solid waste and additive and pH controlling agent are mixed under conditions which support reaction between the additive, pH controlling agent and metals, the metals will be converted to non-leachable forms which are relatively stable under normal environmental conditions. The treatment additives can be introduced and contacted with the soil or waste in any of the following techniques: spreading the additives on top of the soil or waste and mixing with a me~hanlcal device, such as a rotary tiller, .adding the treatment chemical through an infiltration gallery as a solution or slurry, injecting a soluble additive through injection nozzles or injection wells, and adding a treatment additive through a hollow-shaft auger and in-place mechanical mixing. 13 Chdms, 1 Drawing Sheet

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U.S. Patent

Apr. 13, 1993

5,202,033

ZONE CONTAINING LEACHABLE H EAVY METALS DIVIDE THE TREATMENT ZONE INTO A GRID OF UNIFORM TREATMENT UNIT AREAS ~ PLACE QUANTITY OF TRIPLE SUPERPHOSPHATE IN EACH SQUARE DISTRIBUTE THE PLACED " TRIPLE SUPERPHOSPHATE IN EACH SQUARE PLACE QUANTITY OF MAGNESIUM OXIDE WITHIN EACH SQUARE DISTRIBUTE THE PLACED ¯ MAGNESIUM OXIDE WITHIN EACH SQUARE MIX THE DISTRIBUTED TRIPLE SUPERPHOSPHATE AND MAGNESIUM OXIDE ,WITHIN THE TREATMENT

t

AREal.

.Fig.1

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5,202,033

Examples of nonacidie or not heavily buffered acidic IN SITU METHOD FOR DECREASING HEAVY leach tests, commonly referred to as water leach tests, METAL LEACHING FROM SOIL OR WASTE include the Indiana Water Leach Test, which is also called the EP Water I.eaeh Test (Indiana AdministraFIELD OF THE INVENTION 5 tive Code Title 329, Article 2, Solid Waste Management Rule 9); the U.S. EPA Multiple Extraction Procedure This invention relates to the treatment of contami(U.S. EPA, 1986, updated 1991, Test Methods far Evalunated waste or softs in general, and particularly to the ating Solid Wast~ Volume 1C, Method 1320 in.place chemical treatment of wastes or mils containing high levels of heavy metals such as lead, zinc, EPA/530/SW-846); the Synthetic Precipitation Leachsenie, chromium, copper, and cadmium to control 10 ing Procedure (U.S. EPA 1986, updated 1991, Test Methods for Evaluating Solid Wastes. Method 1312, leaching of these heavy metals such that they will not EPA/530/SW.846); the American Society of Testing leaoh at unacceptable levels into the ground water under naturally occurring conditions. Materials Test (ATSM Standards, method D3987-85); the American Foundryman's Society Leach Test (Ham, BACKGROUND OF THE INVENTION 15 R. K., W. C. Boyle and T. P. Kunes, d. Env. Eng. Die. As the potential dangers of hazardous wastes in the Amer. So~ CivilEng., 107 EEL, pp. 155-170, 1981); and environment have become better appreciated, regnla. the University of Wiscousin SLT Test (Ham, R. K., M. tory and.community pressure have made it necessary to A. Anderson, R. Stegman~ and R. R. Stanforth, EPA return to sites of waste disposal or toxic contamination 600/2-79/109, 1979). to reassess the possible hazardousness of wastes or con- 20 For wastes that arenot.disposed of in acidic environtaminants disposed there and to take steps to reduce or ments, two separate leach tests need to be run to detereliminate dangers to people directly or to the surround. mine whether the waste is hazardous according to regning environment in' general and to ground water in latory standards, and to determine whether the waste particular. could pose an aetna/environmental risk when exposed Heavy metals such as lead, arsenic, cadmium, ehro. 25 to nonacidic leaehate in a disposal facility. The TCLP mium, zinc and copper are common elements of con- test will define the regulatory status of the waste. A cern in waste sites under investigation, with lead being water leach test will provide an indication of the actual the most commonly found. Leaching of heavy metals leaching potential of the waste in the environment and into ground water is of particular concern because of whether the the danger that drinking water 'supplies would thus 30 indicate and SMCL's) Drinking Water Regulations (MCL's are being excwded. become contaminated. The U.S. EPA has designated U.S. Pat. Nos. 4,889,640 METHOD AND MIXmaximum contaminant levels (MCL's) and secondary WASTES; maximum contaminant levels (SMCL's) for heavy met. TURE FOR TREATING HAZARDOUS HAZARDals in the National Drinking Water Regulations pres- 4,950,~O9 METHOD FOR TREATING FOR 35 OUS WASTES; and 5,037,479 METHOD ented in 40 CFR §141.11 and §143.3 (1990)0 DUCT!ON OF HEAVY" METAL LEACHING Solid wastes are classified as hazardous by the United States Environmental Protection Agency (U.S. EPA) FROM HAZARDOUS WASTE UNDER ACIDIC for a number of reasons. Certain wastes are ciassified as AND NON-ACIDIC CONDITIONS, are incorporated by reference herein and provide methods and hazardous because they contain chemicals which are listed by U.S. EPA as hazardous. Other wastes are 40mixtures for making wastes non-hazardous according to certain standards prior to deposit in .a waste disposal classified as hazardous because of characteristics of the waste. These characteristics include ignitability, corro- site. Said patents disclose methods for chemically controlling the leaching process in waste. sivity, reactivity, and toxicity. U.S. Pat. No. 4,889,640 describes a method of treating The characteristic of toxicity is determined using the Toxicity Characteristic Leaching Procedure Test 45 solid hazardous waste containing unacceptable levels of (TCLP). The TCLP Test determines whether a solid. leachable metals, such as lead and cadmium. It inehides mixing the solid waste with an agent selected from the waste has unacceptable levels of hazardous substances, group consisting of reactive calcium carbonate, reactive such as heavy metals, which can be leaehad from the magnesium carbonate, and reactive ealcinm magnesium waste by infiltrating leachate. Wastes containing leachcarbonate. After the solid waste and agent are mixed able lead and Cadmium are currently classified as TCLP 50 Toxic Waste if the level of cadmium extracted in a under conditions which support reaction betw~n the TCLp Toxicity test is above 1.0 mg/L or if the level of agent and metals, the metals will be converted into lead extracted is above 5.0 mg/'L. Some states, notably non-leachable forms which are relatively stable under normal environmental conditions. If the solid waste Michigan, also classify wastes which leach high levels of copper and zinc as hazardous. 55 material and agent are both dry when mixed, it may be The TCLP Test is designed to simulate a worst-ease. beneficial to add water to facilitate the mixing of the solid waste and agent and the conversion of the metals leaching situation. These !caching conditions would typically be found in the interior of an actively degrad- into non.leachable forms. The EP toxic wastes were ing municipal landfall. In such landfills, the leaching treated and measured using the EP-toxieity test results medium isslightly aeldie, with a pH of about 5. Addi- 60to determine the amount of leaching of heavy metals tionally, the leaching medium is heavily buffered by after the treatment, The EP hazardous waste criteria was 1.0 mg per liter for cadmium and 5.0 mg per liter volatile organic acids (e.g., acetic acid) produced by the for lead. faeultative anerobie degradation of organic matter. Tests are available which simulate the more typical U.S. Pat. No. 4,950,409 discloses a method of treating disposal situation .fox; hazardous wastes such as foundry 65 solid hazardous waste containing unacceptable levels of waste. These tests utilize a relatively unbuffered solu- leachable metals such as lead and cadmium which intion, e.g., deionized water, to provide a better simula- eludes mixing the solid waste with lime and an agent tion of leaching as it actuatly occurs in the environment. selected from the group of carbon dioxide and blear-

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bonate. After the solid waste and agent are mixed under SUMMARY OF THE INVENTION conditions which support reaction between the agent and metals, the metals will be converted to non-leachaIn accordance with the present invention, an in situ ble forms which are relatively stable under normal envi. -method is disclosed for in-place treatment of disposed ronmental conditions. If the solid waste and agent are S wastes or soils containing unacceptable levels of leachboth dry when mixed, it may be beneficial to add water able materials such as lead, zinc, arsenic, chromium, to facilitate mixing of the solid waste and agent ~nd copper, or cadmium, which may or may not be hazardconversion of the metalsinto non-leachable forms. The ous under U.S. EPA criteria, which includes the steps hazardous waste criterion for the EP toxicity te~t are of mixing or inl'fltrating or injecting the waste or soil 1.0 mg per liter ca~lmium and 5.0 mg p~r Hter for lead. 10w~th at Jea~t one additive that wi~ ch~mJc~y iramobJJi~e.the metals suoh that ahoy'will not leach at unancept. U.S. Pat. No. 5,037,479 discloses a method of treating able levels under naturally occurring condidous or in solid hazardous wastes containing unacceptable levels of leachable metals such as lead, cadmium and zinc lea~hing tests, such ~s a water leach test, designed to which includes mixing the solid waste with a buffering simulate the environment. The treatment is to, cornagent selected from the group consisting of magnesium 15 plashed by m:lding materials containing phosphates or oxide, magnesium hydroxide, reactive calcium carbon- carbonates of greater solubility than the heavy metad, ate and reactive magnesium carbonate, and with an phosphates or carbonates to be formed. Where chroadditional agent which is an acid or salt cont~fing an mium is "present as a heavy metal of concern, the mlditire is ferrous sttlfate..The invention discloses the.steps anion that forms substantially non.leachable forms of the metals or is metallic iron that chemically reduces the 20 of introducing additives which immobilize the heavy metal to a non-leachable form. This anion agent is se- metals by chemical reaction and precipitation in the soil or waste. The phosphate source is selected from the lected from the group consisting of triple saperphosgroup consisting of sodium phosphate, sodium hydrophate, phosphoric .acid, or boric acid, so that under both acidic and non-acidic leaching conditions, the metals 25 gen phosphate, superphosphate, triple superphosphate, phosphoric acid, and polyphosphoric acid. The carbonand mixture will be converted to substantially nonate is selected from the group consisting of sodium leachable forms. The criterion for the leachability uses carbonate, sodium bicarbonate, calcium carbonate, agrithe TCLP toxicity test whereby cadmium is extracted cultural llme, and water softening sludge from municiat a level below 1.0 mg per liter and lead is extracted at pal water softening plants. The phosphate, or carbon. a level below 5.0 mg per liter, and also the water leach 30 ate-containing mater/Ms form insoluble phosphate or test whereby the criterion for cadmium is a level below carbonate salts with" the heavy metals in the soil or 0.01 mg per liter and lead at a level below 0.05 mg per wastes such that the heavy metals wfl] not leach out at liter. Unacceptable levels in the environment or in leaching Common methods for treatment of contaminated tests such as a water leach test designed to simulate the waste sites usually involve excavating the contaminated 35 environment. By "unacceptable" levels is meant levels material and treating it with a solidifying agent such as of contaminants in excess of the MCL's and SMCL's as cement or some form of silicates. However, such treatdef'med in the National Drinking Water Regulations. ment is costly and results in a large volume increase of Where the addition of an additive may cause the release the material. Such methods will sometimes employ a. of a second toxic metal, an additional pH control agent hollow-stem auger for injecting the cement or silicate 40additive may be added to immobilize both the toxic material into the soil and then mixing in place. There is metals simultaneously. The pH control agent additive evidence to suggest, however, that such treatments are adjusts the pH of the lea~hing environment to the range not always effective in preventing the leaching of heavy where the heavy me~ phosphate or carbonate r~ts ~e metals such as lead. (S~e Immobilization Mechanisms n least soluble. The pH control agents are selected from .Solidification/Stabilization of Cd and Pb Salts Using 45 the group consisting of magnesium hydroxide, magnePortland Cement Fixing Agents, Cartledge, et at. Envi-, sium oxide, c~lcium oxide, or calcium hydroxide. The ron. sea. Technol. 1990, Vol. 24, No. 6, pp. 867-873.) additives may be introduced into the surface of the soil Another known method of remediating heavy metal or disposed waste as a ~olid and mixed in by tilling when contaminated sites is to wash the affected soil or waste the soil/waste body is rdufllow, that is one to two feet with a solution and collect the leachate for removal and ~0 deep. Where the waste body is d~p, i.e. greater than disposal. This method has drawbacks of being lengthy two feet, the additive can be introduced as a solution or and expensive, and resulting in a collection of concert- flurry by using an infiltration g~llery, injection wells, an ¯ trated heavy metals which may themselves be hazardinjection no~.le, or by the u~ of a hollow stem auger ous wastes which must be carefully disposed of. with in.place mechanical mixing. Preferably granular Methods which involve excavation and removal of $$ triple superpho~phate and magnesium oxide powder are waste material for treatment are cosily, requiring exca- spread on the soil or waste, raked over the surface for vation and trucking equipment and personnel. Further. uniform distribution and then tilled into the soil or more, due to strict regulations for handling and transwaste. The mounts of triple superphosphate and magport of hazardous wastes and soil contaminated with nesium oxide are in a sufficient qu~tity so that any 100 hazardous waste, even temporarily removing loads of 60 gram ~mple of the mixture has sufficient quantities of soil for treatment above ground and on site may require the additiv.es to limit the heavy meufl lea~hJng to below specific permits or variances. For this reason, a treatthe current Maximum Contaminant Levels (MCL) and ment method which renders waste non.ha2ardous with. the current r,o~ondary MarJ~um ~ontmninant Levels out any excavation is highly desirable. (SMCL) for drinking water as well as the levels which What is needed is a method for treating waste sites 65 will be effective Jul. 30, 1992. containing heavy metals which chemically controls the It is an object of the present invention to provide a leaching of heavy metals and which may economically simple and ec, onomical method of remediating soil and be employed without the need for excavation of the site. disposed waste which avoids excavation.

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It is a further object o.f the present invention to pro~ TABLE 1 vide a simple method of treating solid hazardous disUsed With Other Additix;es/ posed wastes or soil in situ containing unacceptable Additive pH Control Agent levels of leachable heavy metals such as arsenic, lead, Sodium Phosphate Alone cadmium, chromium, copper, and zinc to reduce the Sodium Hydroge~ Phosphate leaching of said heavy metals and render the leachate Superpho~plmte Alone or with , within the primary and secondary Drinking Water RegSodium Ca.,'oonate or Triple Su~h~p~te Ctlcium Carbonate ulatious criteria for those heavy metals. or Magnesium Hydroxide It is also an object of the present invention to provide Ph~hodc A~d OJcium Oxide or an effective treatment method where there are mu/tiple or Calcium Hydroxide heavy metals present by the simultaneous use of a pH Pol~h~phofic Acid Alone or with ~ ~ or control agent additive with the treatment additive to Supe~phos~hate optimize the leaching environment to the pH range Triple Superpho~ph~t~ where the heavy metals are least soluble. Phosphoric Acid or 15 Polyphosphoric Acid It is a further object of the present invention to proFerrou~ Sulfate Alone or with vide a method for treating solid hazardous waste mateM~gnedum Hydroxide, rial cont.a~ing unacceptable levels of leachable metals (for he.xav~lent chromium) Magnesium Oxide, such as arsenic, lead, cadmium, chromium, copper, and C=Icium Oxide or C~l~ium Hy~oxid¢ zinc such that the treatment effectiveness does not de2O crea~ with the age Of the treated waste. Other objects, features and advantages of the invenTable 1 shows, suggested, combinations of additives tion will be apparent from the following detailed deand pH control agents, although other combinations are scriptlon of the invention. possible, depending upon specific heavy metals present BRIEF DESCRIPTION .OF THE DRAWING .25 in the contaminated soil or disposed waste. For a spe. .Cific treatment, the appropriate ratio of additives and FIG. I is a flow chart indicating the steps a preferred pH control agent (if needed) and disposed waste or soil embodiment of the soil or waste treatment method of may be arrived at by experimentation on 103 gram sam. this invention. ples of the disposed waste or soil having various per$0 centages of the additives and pH control agent 0Y DESCRIPTION OF THE PREFERRED needed) by weight. The appropriate ratio of additive EMBODIMENT and pH control agent (if needed) to disposed waste or The present invention is an in situ method of treating soil should be selected so that the heavy metal levels are solid hazardous waste to control leaching of arsenic, well bel0w the MCL's and SMCL's of the EPA's Nalead, cadmium, chromium, copper, and zinc in soil or 35 tional Primary and- Secondary Drihking Water Regnladisposed wasteso as to chemiea]ly immobilize the tions so. that there is a margin of safety. heavy metals so that they wi/l not leach at unacceptable The mixing of the contaminated disposed solid waste levels under naturally occurring conditions. The unand soil with the treatment additive and pH control treated wastes or soils may or may not be hazardous agent additive (if necessary) mast be complete enough under U,S. EPA criteria. The process consists of intro- 40 so that any small sample of the treated contaminated ducing a treatment additive consisting of a phosphate waste or soil (e.g. 100 grams) has sufficient treatment additive or carbonate additive or a chemical reducing additive and pH control agent additive (if necessary) to additive such as a ferrous sulfate into the soil or waste. render it within, the Drinking Water Regulations The treatment additive is then allowed to react with the MCL's and SMCL's criteria when tested using a water soluble heavy metals in the soil to form insoluble phos- 45 leach test. The disposed waste or soil treatment addi. phate or carbonate salts. Where chromium is present, tires and pH control agent additives (if necded) should. the hexavalent soluble toxic chromium !s reduced to the be mixed into a mixture with a sufficient quantity of insoluble trivalent chromium form by the ferrous sulfate such that upon conversion of the metals into non-leachadditive. A second additive, a pH control agent, may be able forms, random 103 gram. samples of the mixture usedin addition to the phospham or carbonate additive ~ wi~ have suffzdent agent to reduce t~e arsenic level to to adjust the pH of the leaching heavy metal environbelow 0.05 rag/L, the lead level to below 0.05 rag/L, ment to the range where the heavy metal phosphate or the zinc level to below 5.0 rag/L, the cadmium level to carbonate salts are the least soluble. In addition, the pH below 0.035 tag/L, the copper level to below 1.0 mg/L control agent may be used with the ferrous sulfate addiand the chromium level to below 0.1-mg/L in the liquid tive to buffer the solution to prevent trivalent chro- 55 extract which is prepared from the sample and analyzed mium salts from sohibilizing. The treatment' additives in a water leach test. are any of the following used individuaJly or in combiIn the preferred ~mbodiment, soIid waste which is nation: sodium phosphate, sodium hydrogen phosphate, classified as hazardous due to high levels of leachable superphosphate, triple superphosphate, phosphoric Ie.afl and arsenic is treated with a combination of granuacid, polyphosphodc acid, sodium carbonate, sodium 60 lar triple superphosphate (TSP) and magnesium oxide bicarbonate, calcium carbonate, agricultural lime, and powder (MgO). The mount of additive and pH control water softening sludge from municipal water softening agent will depend upon the concentrates of the heavy plants. The additives contain anions that precipitate the metal contaminants present. Thus a preliminary screenheavy metals into the soil or waste. Ferrous sulfate can ing chemical analysis must be performed. After the be used to control chromium leaching. The pH control- 65 analysis, a determination must be made of th.~ effective ling agent is selected from the group consisting of mag- ' quantity of additive and pH control agent. Dry mixing nesium hydroxide, magnesium oxide, calcium oxide, of the additive and pH control agent with the contamiand calcium hydroxide. nated materials, i.e., disposed waste or soils, does not

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One or more workers may then proceed to cut open necessarily cause the reactions which convert the lead and arsenic into substantially non-leachable forms. and empty each bag within its own unit area. The triple superphosphate is then distributed uniformly within the The term "non-leachable forms" as used herein unit area by raking it out to a constant depth over the means a form of arsenic,, lead, zinc, cadmium, copper and chromium in the soil or disposed waste that, where 5 unit area surface. subject to the leaching conditions of a water leach test, Next an appropriate quantity of the second additive, will not leach lead at above 0.05 mg/L in a water leach for example, a fifty-pound bag of magnesium oxide, is test leaehate, or arsenic above 0.05 mg/L in a water placed in each treatment unit area, cut open, and distribleach test leachate or zinc above 5.0 mg/L in a water uted by raking over the surface of each unit area. leach test leachate or cadmium above 0.005 mg/L, in a 10 Once the two additives are in plac~ at appropriate water leach test leachate or copper above 1.0 mg/L in levels over the entire zone, the additives are mixed into a water leach test leachate or chromium above 0.I the contaminated soil throughout the zone. mg/L in a water leach test leachate. These leachate The additives are applied in an appropriate mixture leveis are based on the National Drlnki~.g Water Regu- such that the additives, when mixed in the soil or waste, lations current maximum contaminant levels ~CL's), 15 will control lea~hing of the metals using a water leach mw..ondary maximum contaminant levels (SMCL's), and test method. revised MCL's for cadmium and chromium which will The soil and additives may be mixed by a convenbe effecti~,,e Jul. 30, 1992, 40 CFR §141.IICo) (7ri-90 tional walk-behind type rotary tiller. However, a tracEd), 40 CFR §143.3 (7-I-90 Ed) and 56 Fed. Reg. 3528 toe-mounted rotary ti~er is preferable to speed the mix. 20 ing process and reduce operator contact with the soil (1991 Table 1). The reactions may not occur until the contaminated and additive. The treatment zone may be sprayed with material is wetted naturally by rain or snow or until the water if necessary to keep down dust. mixture is analyzed using a leaching test. In appropriate After several passes with the rotary tiller, it will be amounts, the mixture of the first additive, and the see- necessary to draw core samples and to analyze the samond additive, the pH controlling agent, in solid waste 25 ples for treatment effectiveness. will control the leaching of the metals under naturally The phosphate or carbonate containing materials occurring conditions. form insoluble phosphate or carbonate salts with the An example of an application of the method of this the soil or wastes, such that heavy metals invention is the treatment of a zone of soil contaminated heavy metal in out at unacceptable levels in the environwill not leach with lead and arsenic as the result ofthe zone's use as an 30 ment or in leaching tests d~signed to simulate the enviagricultural pesticide mixing area. Such a site, if left ronment. These tests might include water leaching tests untreated, poses a potential hazard of contaminating or simulated acid rain leaching tests. ground water and hence drinking water from heavy ¯ should be be applied ¯ metal leaching. This contamination is of a shallow andItmixed withnoted that the additives mayin any conthe soil or disposed waste 35 depth, approximately one foot. ventional manner, with alternative means for maintainBecause of the classification of the contaminated soll ing quality control and overall coverage. as hazardous, it may not be removed or disposed of The addition of the additives as dry substances with without permitting or variances. By utilizing the surface mixing will be best ul~iz~ where the contamimethod of this invention the contaminated soil is rendered .non-hazardous. After treatment it may be left in 40 nated soil or waste to be remediated is located at relaplace with no significant threat to ground water, or it tively shallow depths, although use of specialized tilling machinery or harrows may allow depths of more than may be excavated and disposed of in a conventional two feet to be treated. manner as non-hazardous waste. For treatment of soils and wastes contaminated to As shown in the flow chart of FIG. 1, after analyzing the waste to determine appropriate amounts of additive 45 depths greater than one to two feet, the additives should required, the treatment zone -- that is the area of. preferably be introduced as solutions or slurries. One ground that is determined to contain amounts of hazard- " method for introducing the additives is through injection wells, with collection and recycle of the leaehate ous heavy metals requiring treatment -- is divided into after it passes through the soil. a grid of uniform contiguous squares. For a particular level of contamination a square of 11 square feet will be ~0 Alternatively, an additive solution may be introduc~ a workable size. Each squaye comprises an individual into the soil or waste through injection nozzles insured treatment unit area. The grid facilitates effective admin- into increasing depths of soil to facilitate contact tween the soil or waste and the treatment additive soluistration of necessary amounts of treatment additives by applicators with no specialized chemical skills. By di- tion. The injection nozzle may have a pointed end with viding the treatment zone into discrete treatment .unit 55 perforations for easy insertion of the nozzle and discharge of the treatment additive into the soil. The addiareas, quality control is maintained by assuring that in treating the zone as a whole no port.ion of the contami- tive solution is forc~l through varying depths of soil by inserting the nozzle to the desired depth and by applicanated ground is overlooked. tion of pressure to the additive solution. One type of Once the appropriate quantity of additives per treatment unit area has been determined, the application of 60 injector would be similar to a root zone irrigator commouly used to fertiliz~ the root zone of trees. the treatment is a straight-forward process. Alternatively the solutions or slurries may be applied After the treatment zone has been determined and through an infiltratiun gallery which applies the soludivided into treatment unit areas, an appropriate quantity of the t'u-st additive, for example a fifty-pound bag tions without disturbing the surface to allow the addiof triple superphosphate, is placed in each unit area. 65 tives .to percolate in solution into the soil or disposed waste where it precipitates at depth. Once each unit area has received a bag of additive, Another alternative in-place treatment may be earcomplete coverage of the zone is easily determined tied out by injecting the treatment additive through the visually.

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shaft of a hollow stem auger and then mixing the soft and additive with the auger.

9

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per liter. In addition, the phosphate lowered the pH of the leaching solution from 11.65 to more acceptable values of pH. TABLE 2 In the third example, Waste 3, a ~oil contaminated IMMOBILIZATION OF HEAVY METALS IN WATER 5 with lead and arsenic was treated with TSP and then LEACH TESTS BY ADDITION OF CARBONATEOR PHOSPHATE-C~NTAINING COMPOUNDS with a mixture of TSP and magnesium oxide. If the 100 gram sample is a mixture containing 5% TSP by EP WATER LEACH TEST R~SULT~ Zinc weight, the level of lead in the EP Water Leach test SAMPLE pH mg/L mg/L mg/L liquid extract is reduced from 1.4 mg/L to 0.11 mg/L Waste 1. treatment of a zinc conteinln8 waste 10 This however caused an increase in the level of arsenic Untreated 6.35 NA NA 570 in the EP Water Leach test liquid extract from 0.012 +5% Sodium 8.85 0.4 mg/L in the untreated, soil to 0.370 mg/L in the treated soil. Treatment with TSP alone, although decreasing + 10% Sodium 10.25 0.5 Carbonate the leachable lead concentration, caused an increase in Waste 2 - ta'eatment of a steel mill waste 15 the leachable arsenic concentration. The pH controlling Untreated 11.65 NA 16.0 1.7 agent, magnesium oxide, was introdue~l to immobilize +5% TSP* 9.45 NA 0.0|6 0.06 both the lead and arsenic simultancously. Once the 5 6.~ HA 0.008 0.27 + 10% TSP Waste 3 - treatmen! of a soil contJtmiaated percent TSP and 5 percent magnesium oxide were with ]e.ad and arsmfic added, the leacklng of arsenic was reduced to well Untreated 7,87 0.012 1.4 NA 20 below the Drinking Water Regulation Standards +5% TSP 5.45 0,3? 0.110 NA (MCL/SMCL's) of 0.05 milligrams per liter for arsenic + 10% TSP 5.04 0.50 0.067 NA and 0.05 milligrams per liter for lead. +5% TSP & 5% MgO 10,2 0.004 0,027 NA Drinking Water -0.05 0,05 5 The fourth example, Waste 4, illustrates the treatment Criteria of an and zinc to which 5% TSP and 10% magnesium (MCL or SMCL) 25 lead, iron foundry waste containing cadmium, copper, oxide were added. If the I00 gram sample is a mixture containing 5% TSP by weight and 10% MgO by weight, the level of cadmium in the EP Water Leach Unlreated ¯ 3.55 0.090 2.5 0.048 '+5% TSP & 10,43 ,001 0.01 0.004 0.05 30 test liquid extract is reduced to weII below the Drinking Water Regulations criterion of 0.005 milligrams per 10% MgO Drinking Water 0,005 1 0.05 liter, the copper level is reduced to well below the Criteria drinking water criteria of 1.0 milligrams per liter, the ('MCL or SMCL) lead level is reduced to well. below the Drinking Water Chromium 35 Regulations criteria of 0.05 milligrams per liter, and the zinc level is reduced to well below the Drinking Water Waste 5 - Treatment of chxomium-containing waste Regulations 5.0 milligrams per liter. Untreated 12.73 8.75 The fifth example, Waste 5, shows the treatment of a . +2.75% FeSO4 12,72 .3.50 chromium containing waste with the additive ferrous +5.0% FeSO4 , 12.68 0.005 + 10% FeSO4 12.62 0,005 , 40 sulphate. In this instance where the 100 gram sample of Drinking Water 0. the waste contains 10% by weight of ferrous sulphate, ¯ Criteria (MCL) leaching of chromium is reduced to weIl below the "NA = mot Drinking Water Regulations criteria (MCL) for ehro**TSP ffi triple supcypho~pha~ mlum of 0.100 milligrams per liter using the EP Water Five examples of laboratory waste treatment of soil 45 Leach test. It is expected that in situ treatment of the waste will samples and disposed wastes containing heavy meta! result in similar reductions of leachable concentrations with specific additives are given in Table 2. By way of of the heavy metals. It is expected that use of these example, untreated waste shown in Table 2 contains concentrations of leachable zinc which exceed SMCL's additives in dry forms, solutions or slurries should all be for drinking water. If the 100 gram sample is a mixture 50 eff~tive. It should be noted that in some c~ses soll or disposed containing 5% sodium carbonate by weight, the level of zinc in the EP Water Leach test leamhate is reduced ¯ wastes containing heavy metals in quantities less than from 570 mg/L to 0.4 rag/L, a drastic reduction and those deemed hazardous by the U.S. EPA will still be well below the SMCL for zinc orS.0 mg/'L. Addition of desirabIy remediated by the process of this invention sodium carbonate materials reduced zinc leaching to55 due to potential ha~.ards to nearby ground water. In those cases the process wLL! be advantageously applied below the water criteria for zinc of 5.0 milligrams per primarily for its simplicity and low cost. liter. Such treatment is used to immobilize zinc in the It is understood that the invention is not comemed to waste such that zinc does not leach out into the sur. the particular process disclosed herein, nor to the materounding environment. In the second example, Waste 2, a steel mill waste was 60 rials and substances described, but embrar~s such modified forms thereof as come within the scope of the fop treated with triple superphosphate. If the 100 gram lowing claims. sample is a mixture containing 5% TSP by weight, the We claim: level of the lead in the EP Water Leach test extract is 1. A method for treating disposed solid waste or soils reduced from 16.0 mg/L to 0.016 mg/L and the level of zinc in the EP Water Leach test extract is reduced from 65 containing unacceptable levels of chromium, the 1.7 mgfL to 0.06 mg!L The treatment reduced the method comprising the step ofmixing the solid disposed leaching to well below the Primary Drinking Water ¯ waste or soil with ferrous sulfate, so that under conditions which support the reaction between the ferrous Regulation standards (MCL) for lead of 0.05 milligrams Cadmium Copper Lead Zinc pH mg/L mg/L mg,/L Wrote 4 - Treatment of" an iron fou~d~ waste

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sulfate and the chromium, the chromium will be con- and calcium hydroxide, so that under conditions which will support the reaction between the additives and the vetted to non-leachable forms which are stable under arsenic, the arsenic will be converted to non-leachable normal environmental conditions. 2. The~ method specified in claim 1 wherein the dis- forms which are stable under normal environmental posed waste or soils and ferrous sulfate are mixed into a ~ conditions. 10. The method of claim 9 wherein the soil or dismixture with a sufficient quantity of the ferrous sulfate posed waste and pH control agent are mixed into the such that upon conversion of the chromium into nonleachable form, random 100 gram samples of the mix- mixture with a sufficient quantity of additives such that ture will have si~fficient ferrous sulfate to reduce the upon conversion of the arsenic into non-leachable chromium level to below 0. I. milligrams per liter in I0 forms, rahdom 100 gram sanaples of the mixture will a liquid extract which is prepared from the sample and have sufficient additives to reduce the arsenic levels to less than 0.05 milligrams per liter in a liquid extract analyzed in accord with a water leach test. 3. The method of claim 1 wherein the ferrous sulfate which is prepared from the sample and analyzed in is mixed with the soil or waste by introdu.cing a solution accord with a water leach test. 15 11. A process for reducing the leaching of copper of ferrous sulfate into the top of the soil. 4. The method specified in claim 1 wherein the fer- from disposed waste or contaminated soil, in a particurous sulfate is mixed with the soil or waste is by intro- lar treatment zone, comprising: . (a) dividing the treatment zone into a grid of treatducing a solution of the ferrous sulfate through an injecment unit areas; tion nozzle, forcing the ferrous sulfate through various depths of a soft or waste by inserting the nozzle to the 20 (b) placing a predetermined quantity of a first additive selected from the group consisting of sodium desired depth within the soil or waste and by applicaphosphate, sodium hydrogen phosphate, supertion of pressure to the ferrous sulfate solution. $. The method of claim I further comprising adding a phosphate, triple superphosphate, phosphoric ,acid, and polyphosphorie acid; pH control agent to the soil or waste in which the ferrous sulfate has been introduced, the pH control agent 25 (e) distributing each quantity of first additive over each treatment unit area; being selected from the group .consisting of magnesium (d) mixing the first additive with the soll or waste of oxide, magnesium hydroxide, calcium oxide and cal. each treatment unit area whereby under environcium hydroxide. mental leaching conditions the copper in the soil or 6. A method of treating soil or disposed s~lid waste disposed waste will be converted into substantially containing unacceptable levels of leachable copper 30 non-leachable forms. comprising the step of mixing the solid waste or soil 12. The process of claim 11 further comprising: with an additive selected from the group consisting of (a) placing a presoribed quantity of a second additive sodium phosphate, sodium hydrogen phosphate, superselected from the group consisting of magnesium phosphate, triple superphosphate, phosphoric acid, hydroxide, magnesium oxide, calcium oxide, and polyphosphoric acid, sodium carbonate, sodium bicar- 35 calcium hydroxide within each unit area; bonate, and calcium ei~rbonate, so that under conditions (b) mixing the first and second additives with the soil' which support reaction between the additive and the or waste of each of the treatment unit areas. copper, the copper will be converted to non-leachable 13. A process for reducing the leaching of arseule forms which are stabl~ under normal environmental 40 from disposed waste or contaminated soil, in a particuconditions. 7. The method of claim ~i further comprising intro- lar treatment zone, comprising: (a) dividing the treatment zone into a grid of treatducing into the soil or waste a second additive for pH ment unit areas; control selected from the group consisting of magne(b) placing a predetermined quantity of a ftrst addisium hydroxide, magnesium oxide, calcium oxide and 45 tive ~selected from the group consisting of sodium calcium hydroxide along with the first additive. phosphate, sodium hydrogen, phosphate, super8. The method of ctaim 6 wherein the soil or disposed¯ phosphate, triple superphosphate, phosphoric acid, waste and the additive are mixed in a mixture with a and polyphosphorie acid; sufficient q~ntity of the additive such that upon con(e) distributing each quantity of first additive over version of the copper into non-leachable forms, random 50 each treatment unit area; 100 gram samples of the mixture will have a sufficient (d) mixing the first additive with the soil or waste of additive to reduce the copper level below 1.0 millieach treatment unit area; grams per liter in a liquid extract whleh is prepared (e) placing a prescribed quantity of a second additive from the sample and analyzed in accord with a water selected from the group consisting of magnesium leach test. hydroxide, magnesium oxide, caefium oxide, and 9. A method of treating, soil or disposed solid waste 55 calcium hydroxide within each unit area; containing unacceptable level of leachable arsenic, (f) mixing the first and second additives with the soil comprising mixing the soil or waste with at least one or waste of each of the treatment unit areas, additive selected from the group consisting of superwhereby under environmental leaching conditions phosphate, triple superphosphate, phosphoric acid, the arseule in the soil or disposed wastes will be polyphosphoric acid, and with at least one pH control 60 converted into substantially non-leachable forms. agent additive selected from the group consisting of ¯ magnesium oxide, magnesium hydroxide, calcium oxide
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sulfate and the chromium, the chromium will be con- and calcium hydroxide, so that under conditions which vertexi to non-leachable forms which are stable under will support the reaction between the additiyes and the arsenic, the arsenic will be convened t6 non-leachable normal environmental conditions. 2. The method specified in claim 1 wherein the dis- forms which ai'e stable under normal environmental posed waste or soils and ferrous sulfate are mixed into a 5 conditions. 10. The method of claim 9 wherein the soil or dismixture with a sufficient quantity of the ferrous sulfate posed waste and pH control agent are mixed into the such that upon conversion of the chromium into nonleachable form, random 100 gram samples of the mix- mixture with a sufficient quantity of additives such that ture will have siffficient ferrous sulfate to reduce the upon conversion of the arsenic into non.leachable chromium level to below 0.1. milligrams per liter inI0 forms, random 1130 gram samples of the mixture will a liquid extract which is prepared from the sample and have sufficient sdditives to reduce the arsenic levels to less than 0.05 milligrams per liter in a liquid extract analyzed in accord with a water leach test. & The method of claim 1 wherein the ferrous sulfate which is prepared from the sample and mudyzed in is mixed with the soil or waste by introdu, cing a solution ~.7.ord with a water leach test. 15 11. A process for reducing the leaching of copper of ferrous sulfate into the top of the soil. 4. The method specified in claim 1 wherein the fer- from disposed waste or ontaminated soil, in a particu. rous sulfate is mixed with the soil or waste is by intro- lar treatment zone, comprising: (a) dividing the treatment zone into a grid of treatducing a solution of the ferrous sulfate through an injecment imit areas; tion nozzle, forcing the ferrous sulfate through various depths of a soil or waste by inserting the nozzle to the 20 (b) placing a predetermined qtumtity of a first additive selected from the group consisting of sodium desired depth within the soil or waste and by applicaphosphate, sodium hydrogen phosphate, supertion of pressure to the ferrous sulfate solution. phosphate, triple super'phosphate, phosph0rie acid, $. The methodof claim I further comprising adding a and polyphosphorie acid; pH control agent to the soil or waste in which the ferrous sulfate has been introduced, the pH control agent 25 . (e) distributing each quantity of fast additive over each treatment unit area; being selected from the group eousistlng of magnesium (d) mixing the first additive with the soil or waste of oxide, magnesium hydroxide, calcium oxide and caleach treatment unit area whereby under environcium hydroxide. mental leaching conditions the copper in the soil or 6. A method of treating soil or disposed s~lid waste disposed waste will be converted into substantially containing unacceptable levels of leachable copper 30 non-leachable forms. comprising the step of mixing the solid waste or soil ¯ 12. The process of claim 11 further comprising: with an additive selected from the group consisting of (a) placing a prescribed quantity of a second additive sodium phosphate, sodium hydrogen phosphate, superselected from the group consisting of magnesium phosphate,¯ triple superphosphate, phosphoric acid, hydroxide, magnesium oxide, calcium oxide, and polyphosphorie acid, sodium carbonate, sodium bicar- 35 calcium hydroxide within each unit area; bonnie, and calcium carbonate, so that under conditions (b) mixing the first and second additives with the soil' which support reaction between the additive and the or waste of each of the treatment unit areas. copper, the copper will be Converted to non-leachable 1;~. A process for reducing the leaching of arsenic forms which are stabl~ under normal environmental 40 from disposed waste or contaminated soil, in a particuconditions. 7. The method of claim 6 further comprising intro- lar treatment zone, comprising: (a) dividing the treatment zone into a grid of treatducing into the soil or waste a second additive for pH ment.unit areas; control selected from the group consisting of magne(b) placing a predetermined quantity of a fast addisium hydroxide, magnesium oxide, calcium oxide and 45 tire selected from the group consisting of sodium calcium hydroxide along with the first additive. phosphate, sodium hydrogen, phosphate, super8. The method of claim 6 wherein the soil or disposed¯ phosphate, triple superphosphate, phosphoric acid, waste and the additive are mixed in a mixture with a and polyphosphorie acid; sufficient quantity of the additive such that upon con(e) distributing mmh quantity of fast additive over version of the copper into non-leachable forms, random 50 each treatment unit me.a; 100 gram samples of the mixture will have a sufficient (d) mixing the first additive with the soil or waste of additive to. reduce the copper level below 1.0 millieach treatment unit area; grams per liter in a liquid extract which is prepared (e) placing s prescribed quantity of a second additive from the sample and. analyzed in accord with a water selected from the group consisting of magnt, inm leach test. hydroxide, magnesium oxide, ¢.~lium oxide, 9. A method of treating, soil or disposed solid waste 55 calcium hydroxide within each unit area; containing unacceptable level of leachable arsenic, (f') mixing the first trod second additives with the soil comprising mixing the soil or waste with at least one or waste of each of the treatment unit areas, additive selected from the group consisting of superwhereby under environmental .leaching conditions phosphate, triple superphosphate, phosphoric acid, the arseniein the soil or disposed wastes will be polyphosphorie acid, and with at least one pH control converted into substantially non-leachable forms. agent additive selected from the group consisting of magnesium oxide, magnesium hydroxide, calcium oxide
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