&EPA United States Environmental Protection Agency EPA/540/SR-93/517 September 1993 SUPERFUND INNOVATIVE TECHNOLOGY EVALUATION Technology Demonstration Summary Toronto Harbour Commissioners (THC) Soil Recycle Treatment Train A demonstration of the Toronto Harbour Commissioners' (THC) Soil Re- cycle Treatment Train was performed under the Superfund Innovative Tech- nology Evaluation (SITE) Program at a pilot plant facility in Toronto, Ontario, Canada. The Soil Recycle Treatment Train, which consists of soil washing, biological treatment, and metals chela- tion, is designed to treat inorganic and organic contaminants in soil. During the demonstration test, soil from a site that had been used for met- als finishing and refinery and petro- leum storage was processed in the pilot plant. The demonstration test results were mixed. The primary developer's claim to produce gravel and sand that met the THC target criteria for medium to fine soil suitable for industrial/com- mercial sites was achieved for the sand and gravel products. The fine soil from the biological treatment process exhib- ited anomalous oil and grease behav- ior and, although exhibiting a significant reduction in polynuclear aromatic hy- drocarbon (PAH) compounds, did not meet the target level of 2.4 ppm for benzo(a)pyrene. This Technology Demonstration Sum- mary was developed by EPA's Risk Re- duction Engineering Laboratory, Cincinnati, OH, to announce key find- ings of the SITE Program demonstra- tion that is fully documented in two separate reports (see ordering infor- mation at back). Introduction In response to the Superfund Amend- ments and Reauthorization Act (SARA) of 1986, the U.S. Environmental Protection Agency (EPA) established a formal pro- gram called the Superfund Innovative Technology Evaluation (SITE) Program. The SITE Program was established to ac- celerate the development, demonstration, and implementation of innovative technolo- gies at hazardous waste sites across the country. The program is a joint effort be- tween EPA's Office of Research and De- velopment (ORD) and Office of Solid Waste and Emergency Response (OSWER). The purpose of the program is to assist the development of hazardous waste treatment technologies necessary to implement new cleanup standards that require greater reliance on permanent rem- edies. This is done through technology Printed on Recycled Paper ------- demonstrations designed to provide engi- neering and cost data on selected tech- nologies. The Toronto Harbour Commissioners conducted an extensive evaluation of this treatment train at a 55 tons/day pilot plant located on the Toronto Harbour Front, Toronto, Ontario, Canada. An EPA SITE demonstration was conducted in April 1992. The SITE project examined, in de- tali, the processing of soil from one of the sites being evaluated as part of the over- all project. The treatment train consists of _, Sand Coal/ Contaminated Soil three processes shown conceptually in ure 1. The first process uses an attrition soil wash process to separate relatively uncontaminated soil from a more heavily contaminated fine slurry. The contaminated fine slurry is then further processed in a metals removal process or a bioslurry re- actor process or both to remove organic and heavy metal contamination. THC has estimated that as much as 2.2 million tons of soil from locations within the Toronto Port Industrial District (PID) may require some form of treatment because of heavy metal, organic contamination, or both. Gravel Feed Hopper ^ ' Trommel Washer V Contaminated slurry to biological treatment Metals Figure 1. Simplified process flow diagram of the Toronto Harbour Commissioners' Soil Recycle Treatment train. The THC claims that the treatment train technology will meet the following perfor- mance criteria: 1. Produce gravel (sized between 0.24 and 1.97 in.) and sand (sized be- tween 0.0025 and 0.24 in.) from the soil washer that will meet the THC target criteria for coarse textured soils described in Table 1 for both organic and inorganic compounds indepen- dent of the initial contaminant levels. 2. Produce a fine soil fraction (sized less than 0.0025 in.) after metals removal or biological treatment or both that will meet the THC target criteria for fine textured soils described in Table 1 for both organic and inorganic com- pounds independent of the initial con- taminant levels. The THC criteria have been developed by THC by combining existing criteria for conventional pollutants and metals with a site-specific criterion developed for a con- taminated soil associated with a refinery site. The goals of this demonstration were to evaluate the technical effectiveness and economics of the treatment process se- quence and to assess the potential appli- cability of the process to other waste and/ or other Superfund and hazardous waste sites. These and other specific critical and noncritical objectives may be found in the Demonstration Plan [1]. This Project Sum- mary summarizes the treatment train's ability to meet the THC target criteria. Procedure The demonstration took place while soil from a site that had been used for metals finishing and refinery and petroleum stor- age was processed in the pilot plant. This soil was expected to exhibit relatively high organic (oil and grease, PAH compounds) and inorganic (heavy metals) contami- nants. EPA's sampling was of relatively short duration, but it was expected that when combined with results of THC evalu- ation, a sound basis for analysis of the technology would be obtained. Soil was fed to the treatment train, and all solid products were sampled. Samples were also taken to allow separate assess- ment of the performance of each process technology, as required. In addition, samples of recycled water streams and air emission streams were obtained to de- termine the fate of contaminants. Process flow data were accumulated to allow the development of an estimated mass bal- ance for the soil wash process. The data collected during the demon- stration were used to determine the fol- lowing: ------- Table 1. THC Target Criteria for Selected Parameters for Soils to be Used for Commercial/Industrial Lands THC Target THC Target Medium Parameter Course Textured So/7* & Fine Textured Soil Feed' Soil Gravel* Sand" Fine* Soil Conventional Oil and grease (%) TRPHS (mg/kg) Total Metals (mg/kg) Copper Lead Zinc 225 750 600 Organic Compounds (mg/kg) Naphthalene 8.0" Benzo(a)pyrene 2.4 ** 300 1000 800 8.0" 2.4 ป 0.82 2500 18.3 115.0 82.5 11.2 1.9 0.33 800 0.22 620 2.5 5400 6.4 13.8 84 45.3 46.0 548 46.0 34.0 343 2.5 0.6 2.1 0.5 1.3" (2.6) ฎ Defined as greater than 70% sand and less than 17% organic matter. Average of six composite samples. Average of six samples from bioslurry reactor batch 2. Total recoverable petroleum hydrocarbons. If these trigger levels are exceeded, the Ministry of the Environment will make a determination on a case-by-case basis regarding the need for remediation. Values reported are estimated detection limits for this parameter. Cleanup levels are shown for organic compounds. If soils exceed these levels, then the soil is considered hazardous and remediation is required. Values shown are below quantitation limits for procedures. Values shown are estimated. the quality of the gravel, sand, and fine soil relative to the THC target criteria, the percent removal for organic con- taminants (oil and grease, total re- coverable petroleum hydrocarbons (TRPH), naphthalene, and benzo- (a)pyrene) from gravel, sand, and con- taminated slurry for the attrition soil wash process, the percent removal of organic con- taminants from a soil slurry for the bioslurry reactor process, and the percent removal of heavy metals (copper, nickel, lead, and zinc) for a soil slurry being processed in the met- als removal process. Soil Wash Process Because the majority of contaminated soils encountered at the PID are sandy, silty soils, soil washing (Figure 1) is an economical and effective process to sepa- rate contaminants from the bulk of the soil. A scrubbing action and selected chemicals are used to separate contami- nants from the larger soil particles. The rotary trommel washer removes particles larger than 0.24 in. as a gravel fraction. The contaminated soil particles less than 0.24 in. and the washwater pass through the screen in the trommel washer into a holding tank where belt-type oil skimmers remove free oil from the water. The re- maining soil and washwater are pumped through a separation hydrocyclone where the contaminated fines (less than 0.0025 in.) are separated from the coarser soil particles. Larger sand particles are easily separated from the fines, where the con- taminants are concentrated. The fines are pumped to a lamellar separator and then to a gravity thickener, while the coarse sand is pumped to the attrition scrubbers. Three attrition scrubbing cells agitate the soil particles, causing them to rub against each other and scrub the fine par- ticles and contaminants from the surfaces of the soil particles. Detergents or surfac- tants and acids or bases, if required, may be added to the third cell to aid in dislodg- ing contaminants from the soil particles or in dissolving certain contaminants. The treatment processes subsequently used to treat the contaminated slurry restrict the types of chemicals that can be used in this treatment train. Scrubbed particles and washwater from the attrition scrubbing units are pumped to a second hydrocyclone at the top of the plant, where sand particles (>0.0025 in.) are separated from the process water and the remaining fines. The sand stream from this separator is then put through a den- sity separator to remove the light materi- als, such as coal, wood, and peat particles from the heavier soil particles. The coal and peat are collected separately, as a potentially contaminated waste stream. The sand is discharged by conveyor to a collection bin and is combined with the gravel from the trommel washer for return to the original site. This washed material is expected to include approximately 70% to 80% of the soil feed to the wash plant. Contaminated fines with a grain size smaller than 0.0025 in. pass through the lamellar separator and sludge thickener to remove water. The contaminated slurry from the sludge thickener is fed into two large holding tanks at the front end of the metals removal system or directly to the bioslurry reactor process. The contami- nated slurry is expected to represent ap- proximately 15% to 30% of the soil feed to the wash plant. The contaminated process water re- moved by the lamellar separator and sludge thickener is discharged to an out- door storage pond for recycle. Any sludge recovered from the ponds is then added to the deep cone sludge thickener where it joins the slurry for further treatment. Bioslurry Reactor Process The bioslurry reactor process (Figure 1) involves a series of reactors (tanks) where organic contaminants are treated. Before introduction into the reactor, the slurry is pretreated with a proprietary inorganic oxi- dant. The slurry to be treated is gently mixed in two surge tanks to prevent particles from settling and then pumped to one of three 20,000-gal upflow bioreactor tanks where submerged pumps and the upflow of air from the medium to fine bubble aerators provide constant mixing condi- tions and the suspension of fines. The biological system is prepared for each soil to be treated by inoculating the system with bacteria that have developed in the soil; that is, a limited amount of fine slurry obtained from the soil wash process is pumped directly to the bioreactors with- out passing through the metals extraction process where the highly acidic condi- tions would destroy the desired bacteria. This allows a bacterial population in the bioreactor to developa population based on strains in the soil to be treated. Fine slurry is accumulated until a single reactor is fully charged. Nutrients in the form of urea and phos- phoric acid solutions are added periodi- cally, and oxidants may be added. Once the organics content of the slurry is reduced to a level below the THC guide- lines for industrial soils, the slurry is re- turned to the excavation site since the dewatering process originally selected did not produce a solid product. The developer of this treatment train had planned to use a continuous process for the biological treatment system, but earlier experience with the bioslurry reac- ------- tor process disclosed variable analytical results. Because the developer had not moved beyond batch evaluations at the time of the SITE demonstration sampling, the discharge from two bioslurry reactor batches was extensively sampled. Metals Removal Process The contaminated slurry from the attri- tion wash plant or the bioslurry reactor process is fed into two large holding tanks in the central area of the facility, at the front end of the metals removal process (Figure 1). The slurry consists of approxi- mately 24% solids by weight and 76% process water. Mild acid is added to the slurry from the acid storage tanks to des- orb and solubilize any metal contaminants from the soil particles. The contaminated slurry is then pumped Into the first tubular reactor. This screw- type rotary reactor brings the slurry into countercurrent contact with solid metals chelating agents that have an affinity for specific metal contaminants. From here, the slurry, which now contains only soil particles, organic contaminants, residual metals not removed by the process, and process water, is pumped to a holding tank, where it is neutralized. The solid chelating agent, which moves countercurrent to the slurry, now contains the extracted metals. The solid chelating material is selected from a family of metal- specific, ion-exchange chelating resins to preferentially remove heavy metals. It is washed to remove solid soil particles and is fed through a second tubular reactor where a mild acid breaks the bond be- tween the chelating agent and the con- taminant metals. The chelating agent is then recycled to the first reactor for reuse in the metals extraction process. Mean- while, the metals/acid mixture is recycled in the second reactor until it becomes sufficiently rich in metal to be pumped to an electrowinnlng unit, where the metals are removed by electrolysis. The result of the buildup of metal concentration in the regenerating acid will somewhat reduce the absorption capacity of the resin beads being returned to the slurry contractor. The system has, however, been designed to provide excess absorption capacity of the chelating resin in relationship to the metals being absorbed. Little change in performance is expected. Another, more long-term deterioration of the resins ab- sorption capacity is associated with the oxidation of the active sites on the resin bead. This reaction is expected to be mea- sured In months to years and should not affect this demonstration. Nevertheless, resin replacement costs can be a signifi-, cant cost factor in such a system. The metals may be removed singly or as one composite mass. During electrowinning, the metal-depleted acid is pumped back to the holding tanks for reuse as regener- ating acid, or it may be neutralized and become a part of contaminated slurry. Results and Discussion Soil Product Criterion The gravel (sized between 0.24 and 1.97 in.) and sand (sized between 0.0025 and 0.24 in.) products met the THC target criteria. Fine soil did not .meet the THC target criteria because oil and grease and benzp(a)pyrene levels exceeded the criteria. Soil Wash Process For gravel, removal rates for organic contaminants (oil and grease, TRPH, naphthalene, and benzo(a)pyrene) were 67% or greater. This gravel ac- counted for 11.5% of total process mass output and 4% or less of the organic contaminants in the product streams. For sand, removal rates for organic contaminants (oil and grease, TRPH, naphthalene, and benzo(a)pyrene) were 78% or greater. This sand ac- counted for about 68% of the process output and 15% or less of the organic contaminants in the product stream. The process concentrated the organic contaminants into a contaminated fine slurry (<0.0025 in.) which accounted for about 19% of the process output mass and 74% or more of the or- ganic contaminants. The process also produced a con- taminated coal/peat product (<0.24 in; >0.00025 in) that represented about 1.6% of the process output and 6% or more of the organic contaminants. This waste stream will require dis- posal (most likely by incineration). The feed soil exhibited low heavy- metals contaminant levels (copper, 18 ppm; lead, 115 ppm; and zinc, 83 ppm). The wash process concentrated these contaminants in the fine slurry (19% of the process mass output and 59% or more in the process output streams).' Data from the soil wash process that were developed during the SITE demon- stration are presented in Table 2. Bioslurry Reactor Process When inlet samples were compared with outlet samples, the oil and grease reduction from the bioslurry process was limited. ' A similar comparison for other pa- rameters yielded the following reduc- tion: TRPH, 52%; naphthalene, at least 97%; and benzo(a)pyrene, ap- proximately 70%. Results for the bioslurry reactor pro- cess are shown in Table 3. Metals Removal Process The levels of metal contamination ac- tually encountered eliminated the need to use the metals removal process for this soil. Limited data were developed for the efficiency of the metals re- moval process by sampling a process run of a metal-rich slurry from an- other soil. The reactor achieved the following removal efficiencies based on metals concentrations in the inlet versus the outlet samples: copper, 96%; lead, 71%; nickel, 71%; and zinc, 63%. Because the metals removal process became fouled with oil and grease, the operation shut down prematurely. This may be a limitation on the pro- cess in that slurries with free oil and grease cannot be processed. Results for the metals removal process are shown in Table 4. Fine Product Dewatering Because the hydrocyclone device used for final dewatering of the fine soil was not successful, the final prod- uct from the process was a slurry. Dewatering will require further evalu- ation by the developer or the applica- tion of other technology. Emissions Assessment Emission sampling of the ventilation system serving the biological treat- ment system did not detect PAH com- pounds, but detection limits were very high due to a high concentration of light hydrocarbons in the exhaust stream. These light hydrocarbons . were tentatively identified as a pe- troleum distillate in the range be- tween diesel oil to Stoddard solvent (C9 - C16 paraffins). Total gaseous, nonmethane organic compounds were detected at levels that indicated 220 Ib/day of emissions. (The data illustrate that significant air stripping is occurring in the bioreactor, and this must be accounted for in the design.) The facility has a biological filter sys- tem and carbon adsorption bed in place to control these emissions. ------- Table 2. Selected Feed and Product Characteristics of the Attrition Soil Wash Process Characteristic Feed Soil' THC Criteria Gravel, * <1.97in. X).24 in. Coal/Peat Fraction, * <0.24 in. Sand, * <0.24 in. >0.0025in. Contam. Fines, * <0.0025 in. Percent of output based on site demo data Percent of output based on THC overall analysis 11.5 10.5 1.6 2.5 68.1 70.2 18.8 16.7 Oil, grease (mg/kg) TRPH (mg/kg) Copper (mg/kg) Lead (mg/kg) Zinc (mg/kg) Naphthalene (mg/kg) Benzo(a)pyrene (mgfcg) 8,200 (6,708-9,700)* 2,500 (2,270-3,430) 18.3 (9.2-42.2) 115 ' (63.3-127) 82.5 (40.4-181) ' 11.2 (5.3-18) 1.9 (0.9-2.9) 10,000 225 750 600 8 2.4 3,300 (1,200-10,400) 800 (270-1,370) 6.4 (0.7-12.1) 45.3 (3.2-117) 46 (2.3-98.6) 2.5 (0.9-2.9) 0.6 (0.2-1.0) 38,000 (17,600-51,600) 11,900 (4,760-16,280) 32.9 (22.8-41.7) 406 (12.9-749 210 (46.8-406) 64 (34-110) 14.5 (9.6-23) 2,200 (1,400-3,900) 620 (380-960) 13.8 (32-32.4) 46 (23.6-82.9) 34.1 (15.9-71.4) 2.1 (1.5-3.1) 0.5 (03-1.2) 40.000 (26,900-50,500) 14.000 (8,500-19,800) 83.1 (48.2-135) 522 (421-680) 344 (192-593) 51.7 (17-82) 10.0 (9.0-12.0) Average of six composite samples. * Average of three composite samples. * Range of results. Conclusions The results of the SITE Demonstration Test showed that Soil washing effectively produced clean, coarse soil fractions and con- centrated the contaminants in the fine slurry. The chemical treatment process and biological slurry reactors achieved at least a 90% reduction in simple PAH compounds such as naphthalene but Table 3. Selected Feed and Product Characteristics of the Bioslurry Reactor Process Characteristic Oil, grease TRPH Naphthalene Benzo(a)pyrene MOE Criteria 1.0% 8 mg/kg 2.4 mg/kg Contaminated Fine Slurry ' 4.00% (2.7-5.4) * 1.4% (.85-1.98) 5 1.7 mg/kg (17-82) 10 mg/kg (8.4-12) Bioslurry Reactor Batch 1 * 4.98% (3.96-6.08) .78% (68-.9S) <14 "mg/kg 3. 1 mg/kg (2.0-5.1) Bioslurry Reactor Batch 2* 2.53% (3.98-2.17) .54% (.39-.76) <1 3 "mg/kg <16~i11 2.6 mg/kg (2.3-3.4) Removal Efficiency %* 6 52 97" 71 Average of six composite samples. Average of 6 samples taken at20-min intervals during discharge of batch. Removal efficiency based on average value for both batches. Range of results. Value reported is average ofquantitation limit reported. Detection limit is at least a factor 10 less than the quantitation limit. Removal efficiency calculated from detection limit; estimated by dividing quantitation limit by 10. fell just short of the approximately 75% reduction in benzo(a)pyrene re- quired to achieve the THC criteria. The biological process discharge did not meet the THC criteria for oil and grease, and the process exhibited vir- tually no removal of this parameter. The developer believes that the high outlet oil and grease values are the result of the analytical extraction of the biomass developed during the pro- cess. The hydrocyclone dewatering device did not achieve significant dewater- ing. Final process slurries were re- turned to the excavation site in liquid form. The development of an accept- able dewatering process will require further evaluation of alternative tech- nologies. The metals removal process equip- ment and chelating agent were fouled by free oil and grease contamination, forcing the premature curtailment of sampling. This establishes a limita- tion for this technology since biologi- cal treatment or physical separation of oil and grease will be required to avoid such fouling. ------- Tablo 4. Selected Heavy Metals Date for Removal of Metals from the Liquid Stream by the THC Metals Removal Process Influent Metal mgfag Copper 51.1 (492-532)' Lead 100.5 (942-112) Nickel 11.7 (10.7-12.7) Zinc 277 (264-294) Effluent mg/kg Removal % 1.8 96 (0.9-3.0) 29.0 71 (13.5-46) 3.3 71 (0.9-7.3) 101 63 (53-183) References 1. Science Applications International Corporation. March 16, 1992. "Dem- onstration Plan for the Toronto Harbour Commissioners (THC) Soil Recycle Treatment Train." . Range of values. .S. GOVERNMENT PRINTING OFFICE: 1993 - 750-071/80051 ------- ------- The EPA Project Manager, Teri Richardson, is with the Risk Reduction Engineering Laboratory, Cincinnati, OH 45268 (see below) The complete report, entitled "Technology Evaluation Report; Toronto Harbour Commissioners (THC) Soil Recycle Treatment Train," (Order No. PB93- 216087; Cost: $27.00, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 A related report, entitled "Toronto Harbour Commissioners (THC) Soil Recycle Treatment Train; Applications Analysis Report," EPA/540/AR-93/517, dis- cusses application and costs. The EPA Project Manager can be contacted at: Risk Reduction Engineering Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 Official Business Penalty for Private Use $300 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 EPA/540/SR-93/517 ------- |