&EPA United States Environmental Protection Agency EPA/540/S5-91/003 March 1992 SUPERFUND INNOVATIVE TECHNOLOGY EVALUATION Technology Demonstration Summary BioTrol Soil Washing System for Treatment of a Wood Preserving Site A SITE Program demonstration of one configuration of soil washing process developed by BioTrol, Inc., was carried out at the MacGillis and Gibbs wood treatment facility in New Brighton, MM. The processing train, so called BioTrol Soil Washing System (BSWS), con- sists of three units: . • The Biojrol Soil Washer (BSW) - a volume reduction process, which uses water to separate contami- nated soil fractions from the bulk of the soil. • The BioTrol Aqueous Treatment System (BATS) - a biological water treatment process. • The Slurry Bioreactor (SBR) - a Bio- Trol biological slurry treatment process conducted in an EIMCO BIQLIFT1"1 reactor. At the MacGillis and Gibbs site, where pentachlorophenol (penta) and poly- nuclear aromatic hydrocarbons (PAHs) are the contaminants of primary con- cern,'the BSW separated the feed soil into relatively uncontaminated sandy fraction that accounts for the majority of the feed soil, contaminated woody fractions, and a small fraction of fine clay and silt particles. Contaminant re- moval, defined by the difference be- tween the concentrations of penta in the feed soil and the washed soil, was between 87% and 89% in tests with soil with low penta content (130 mg/kg) and high penta content (680 mg/kg). For total PAHs the removal efficiencies were 83% and 88% in the two tests. The process is particularly attractive where the washed soil material would meet site-specific regulatory requirements for return to the site without further treat- ment. The BATS, using a penta-specific Fla- vobacterium, degraded between 91% and 94% of the penta in the process water from the two soil washer tests. PAH concentrations were below detec- tion limits and removals could not be determined. The contaminated fines are only a small fraction of the original feed soil (<10%) at this site but contain over 50% of the original penta mass. Bio- logical treatment of the slurry of these fines in the SBR required a longer-than- expected acclimation period. Conse- quently, it can only be estimated that removal levels for penta and PAHs of Printed on Recycled Paper ------- over 90% can be attained once steady- state operation is achieved. Costs were estimated for an inte- grated, commercial-scale system and also for each process operating inde- pendently. Incineration of woody mate- rial segregated by the soil washing ac- counts for the major portion (76%) of the costs. This Summary was developed by EPA's Risk Reduction Engineering Laboratory, Cincinnati, OH, to announce key findings of the SITE program dem- onstration that is fully documented in two separate reports (see ordering in- formation at back). Introduction The Superfund Innovative Technology Evaluation (SITE) Program was instituted in 1986 to promote the development and application of innovative technologies to Ihs remediation of Superfund and other sites contaminated wilh hazardous wastes. The National Priorities List (NPL) includes 56 sites contaminated with penta and creo- sote-derived PAHs from wood preserving practices. Soil washing and subsequent biodegradation of the organic contaminants at such sites potentially could be an at- tractive means for remediation of such sites and, consequently, an appropriate topic for investigation under the SITE Pro- gram, This Project Summary highlights the re- sults of an evaluation of a specific ar- rangement of the three technologies of the BSWS. The system consists of mul- tiple stages of physical abrasion, attrition, flotation, and washing of excavated soil in the BSW. This is accompanied by biodeg- radation of solubilized contaminants in the BATS and btodegradation of contamina- tion adhering to fines in the SBR. While the BATS was compatible with the BSW in capacity, the SBR unit provided by Eimco was considerably smaller. The site selected for the evaluation is a wood preserving facility in New Brighton, MN, where creosote and penta were used for several decades. The facility, owned and operated by the MacGillis and Gibbs Company, is currently using the newer chromated copper arsenate (CCA) pre- servative and improved technology to mini- mize site contamination. Process Description Soil previously excavated from two ar- eas on the site was used to provide test soils with two levels of penta contamina- tion. The weighted average concentrations of panta in the two soils were 130 and 680 mg/kg. In the proprietary BSW process, the soil is first screened to remove large material. It is then subjected to slurrying with water, froth flotation, attrition/classification, thick- ening, and dewatering using a combina- tion .of vibrating screens, a mixing trommel, flotation and attrition units, hydrocyclones, spiral classifiers, and dewatering centri- fuges. The test units are mounted on a 42-ft semi-trailer with drop-down sides. It is readily transportable to a site for evalu- ation. With this sequence, the soil is seg- regated into a large volume of relatively uncontaminated sandy material called washed soil, contaminated woody debris, and a much smaller fraction of contami- nated fines. The washed soil is dewatered and returned to the site if in compliance with required cleanup levels, which were not known for this site. Process water from the BSW is treated at a rate of 10 L/min (3 gpm) in the BATS, a multiple-stage fixed-film bioreactor. In- digenous bacteria are supplemented with a penta-specific Flavobacterium to accel- erate biodegradation. The system is first acclimated for about 2 wk by recycle of contaminated water. Nutrients are added and the pH and temperature are adjusted automatically as needed. Air is injected at the base of each bioreactor cell through a series of sparger tubes. The design of the BATS is such that a minimum of operator attention is required. The fines produced by the BSW can be dewatered and disposed of by conven- tional technology such as incineration. An attractive alternative is aerobic biodegra- dation in a 3-stage, stirred SBR operating in a cascade mode. A growth of both indigenous and a penta-specific Flavobacterium are acclimated for at least 1 wk to prepare the system but it was found that the acclimation period is de- pendent on penta concentration. For the demonstration, slurry was diverted to a storage tank during the soil washing of the more highly contaminated soil (680 mg/kg penta) and then fed to the small scale SBR unit (180 L capacity) over a 14-day test period at a flow rate of 24 ml/ min. Membrane diffusers provide the nec- essary air for aerobic treatment. Tempera- ture and pH are automatically controlled. Woody debris, also containing signifi- cant levels of penta and PAHs, is contain- erized for disposal by conventional tech- nology such as incineration. Test Program Tests established that most of the con- taminants (penta and PAHs) are associ- ated with the fine particle fraction of the soil, making the BSW process well suited for concentrating the contaminants in a small fraction of the feed soil. Particle size and contaminant distribution for the vari- ous output fractions from the BSW pro- cess are also provided.. However, these results cannot be related directly to the operation of the BSW. The BSW is designed to operate con- tinuously. For this demonstration, tests were carried out using two soil piles. The first test used a feed soil with a weighted average penta concentration of 130 mg/ kg (average penta: 112.8±19.8 mg/kg) and lasted about 50 hr. About 11,000 kg of contaminated soil was treated. The sec- ond test was carried out over about 150 hrs, with a total of about 18,000 kg of feed soil containing a weighted average of 680 mg/kg penta (average: 657.8 ± 228 mg/ kg) treated. Average throughput rates in the two segments of the study were 220 and 160 kg/hr, respectively. During each test, the different output solids and the process water were weighed and sampled for extensive analyses, in- cluding penta, PAHs, metals, dioxins, oil/ grease, TOG, chloride, organic halide, sol- ids content, etc. All sampling and analy- ses during the demonstration program fol- lowed approved EPA or Standard Method protocols. Flow rates for the input and output streams were calculated using mea- sured differences in the output over time increments. The water used to slurry the soil for processing consisted of varying ratios of municipal water, an aqueous solution of polymer used to thicken the fines stream, and treated effluent from the BATS. The volumes of these were also measured to establish an overall material balance. The water from the BSW process was ana- lyzed for parameters similar to those noted above, both as produced and before it was introduced into the BATS. The efflu- ent from the BATS was also carefully ana- lyzed to establish contaminant removals attributable to the biological action. Similarly, the contaminated fines slurry was analyzed before and after treatment in the SBR. In this case, because of the solids in the slurry (~11% solids), the solid and liquid phases of the slurry were ana- lyzed separately for the critical param- eters (penta and PAHs). Results Predemonstration particle size and con- taminant analyses indicated that the fines, constituting 5% to 8% of the combined output mass, contained approximately 30% of the penta and PAH contamination in the output streams. .However, the proce- dures used in these tests do not allow the results to be related directly to the segre- gation achieved in the BSW. ------- BloTrol Soil Washer , Wide fluctuations in the feed soil rate were encountered during the soil washing of both soil piles due to mechanical prob- lems and the consistency of the soils. Nevertheless, the BSW succeeded in seg- regating the feed soil into relatively uncontaminated washed soil, contaminated woody debris, and a slurry of contami- nated fines amounting to only a small percentage of the feed soil mass. Con- siderable penta is also dissolved into the process water. Removal efficiency was defined by the developer as: % Removal efficiency = - 100 x (1 - washed soil conc.^ feed soil cone. On the basis of weighted average penta concentration in the washed soil versus penta in the feed soil, the removal-effi- ciency was 89% in the test with the low penta concentration' soil and 87% in the test with the high penta concentration. Within each test of the soil washer, the concentration of penta retained by the washed soil remained relatively constant (9% and 11% of output, respectively). In addition, the mass and penta content of the washed soil remained relatively uni- form, regardless of fluctuations in feed soil flow rate or input penta concentration, suggesting that maximum removal had been achieved from that soil. In the two tests, the bulk of the penta in the output streams was found in the fine silt and clay fraction (34% and 27%, respectively), the process water (40% and 34%, respec- tively), and the coarse and fine woody material (14% and 29%, respectively). Weighted values were used for stream masses and penta concentrations in cal- culating masses because sampling inter- vals varied and different masses were col- lected during the different sampling peri- ods; consequently standard deviations could not readily be calculated and would not have the usual meaning. Arithmetic averages and standard deviations for stream flows, masses, and penta concen- trations which indicate that the two calcu- lation methods do not provide greatly dif- ferent results are provided in the report. Mass balances for input and output streams and, particularly for penta con- centrations, varied widely in the two tests with considerably higher combined masses found in the output streams than in the input. While the explanation for this is not certain, there is some reason to believe that the soil washing improves the acces- sibility of the solids during the solvent extraction step of the analyses. Summa- ries of the results for the two tests are presented in Tables 1 and 2. The full report provides more,extensive data on concentrations and masses. Results with PAHs paralleled those ob- served for penta except that much smaller concentrations were found in the process water, which is consistent with the lower solubility of the PAHs. The silt and clay fraction contained 61% of the PAHs in the low penta soil washing test and 55% in Table 1. Results of Low Penta Soil Washing Test the high penta soil washing test while the washed soil retained slightly more PAHs than penta (18% and 15%, respectively). Removal efficiencies in the two tests were calculated to be 83% and 88%. In addition to the copper, chromium, and arsenic expected from the CCA wood treatment now in use, analyses were car- ried out for a number of other metals. Removal efficiencies for copper, chromium, Input Feed Soil Municipal Water Thickener Sol'n Total Output Washed Soil Coarse Oversize Fine Oversize Fine Particle Cake Combined Dewatering Effluent -. Total % Removal Efficiency As-is wt. kg 1.00 5.45 0.82 7.27 1.18 0.14 0.06 0.22 5.00 6.60 Penta cone ppm 130 0 0 14 170 96 270 14 175.5 89 mg 130 0 0 130 16.5 23.8 5.8 59.4 70.0 mass' %* 100 0 0 9 13 3 ' 34 40 Total PAHs cone ppm 247 0 0 42 309 208 778 0.5 83 mass' mg 247 0 N/A 247 49.7 -44.9 12.3 170 '. 2.5 279 %* 100 18 16 4 61, 1 ' Mass refers to the mass of contaminant in the as-is weight of each fraction obtained from treatment of 1 kg of feed soil. 2 Refers to percent of total input or output, respectively. Table 2. Results of High Penta Soil Washing Test Input Feed Soil • Municipal Water Thickener Sol'n BATS Effluent Total Output Washed Soil Coarse Oversize Fine Oversize Fine Particle Cake Combined Dewatering Effluent Total %Removal Efficiency As-is wt. kg 1.00 0.22 0.75 4.12 6.09 1.31 0.18 0.06 0.22 4.50 6.27 cone ppm, 680 0 0 2.8 691.5 87 1400 900 1300 80 87 Penta mass' mg %* 680 0 0 11 114 252 54 286 360 1066 98.3 0 0 1.7 11 24 5 27 34 cone ppm 404 0 0 0.2 48 535 463 1064 1.9 88 Total PAHs mass' mg 404 0 N/A 0.9 405 61.8 92.2 25.8 230.5 8.6 419 %2 99.7 0.3 15 22 6 55 2 ' Mass refers to the mass of contaminant in the as-is weight of each fraction obtained from treatment of 1 kg of feed soil. - , 2 Refers to percent of total input or output, respectively. ------- and arsenic were in the range of 48% to 70% (based on concentrations in feed soil and washed soil). Barium, lead, and mer- cury were the only metals found at signifi- cant concentrations in the output streams. Once again, the fine particle cake con- tained the bulk of the mass of each metal for which sufficient data were available. Similar results were obtained for Total Organic Carbon (TOG) and Total Recov- erable Petroleum Hydrocarbons (TRPH), with removal efficiency from the feed soil of 84% and 94%, respectively, in the test Using the low penta concentratbn soil and 81% and 92%, respectively in the test with the high penta concentration soil. It should be noted, however, that the ranges on which these averaged values are based are broad, perhaps reflecting the variabil- ity in the sampling of the soil washing. Analyses were also carried out on the feed soil and each output stream for vari- ous polychlorodibenzo-p-dioxins and furans(CDD/COFs). The octachtorodibenzo dfoxin (OCDO) isomer constituted about 65% of the congeners found at measur- able concentrations in each soil, and the ratios of congeners were essentially con- stant for all streams. Again, most of the CDD/CDFs concentrated in the Fine Par- ticle Cake and distribution among the out- put streams was similar to that found for the PAHs, Removal efficiencies, based on washed soil and feed soil concentrations of total CDD/CDFs, were 92% in the test with the tow penta concentration and 97% in the test with the high penta soil. BloTroI Aqueous Treatment System Both tests of the BATS were carried out at flow rates of about 10 L/min. Calcu- lated on the basis of flow-weighted mass data, the weighted penta concentrations in the BATS using process water from the low penta concentratbn soil washer test decreased from about 14 to 1.3 mg/L, equivalent to a removal of about 91%. In the test using process water from the high penta concentration soil washing, weighted influent penta concentrations of 44 mg/L were reduced to 3 mg/L, or a 94% re- moval. Analytical data for free chloride production and organic chloride consump- tion were insufficient to establish that the toss of penta occurs by mineralization to chloride, carbon dioxide, and water. Insuf- ficient data for PAHs above the detection limits precluded the estimation of removal efficiencies on the basis of these tests; only acenaphthene was found regularly in influent and effluent. Analyses for metals indicated that there was some decrease during the course of biotreatment. Since none Is expected, it may be presumed that metals are adsorbed in/on the bio- mass in the reactor. Slurry Bioreactor The SBR operated at 24 mL/min (0.38 gal/hr), which provided a retention time of about 5.2 days. Problems were encoun- tered with the feed of slurry due to cold ambient temperatures, with variability in feed concentrations (probably due to poor mixing in the storage tank), and with inad- equate nutrient feed for the unexpectedly high penta concentrations during the ini- tial days of operation. The solid phase of the slurry that was introduced to the SBR contained an average of 2570 ± 506 mg/ kg penta while the liquid phase contained only 59 ± 19 mg/L. Because of these problems and the delay in system re- sponse to corrective actions, acclimation was not achieved before sampling was initiated and initial effluent concentrations of penta and PAHs were higher than ex- pected. Only toward the end of the 14 day test period were the anticipated penta and PAH removal levels of 90% reached for both solid and liquid phases of the slurry. PAHs were not detected in the liquid phase of the influent or the effluent. Even for the solid phase, many of the PAH data were at or below detection and could only be estimated. The high penta concentra- tions in all the samples contributed to the analytical difficulties and high detection limits. Removal efficiencies calculated for each of seven PAHs using measured or estimated concentrations in the solid phases confirmed that removal was pro- ceeding slower than expected and only attained values in the 90% or higher range after about 7 days. For some of the PAHs, removal efficiency never reached this level (Table 3), and for others the highest level was reached early in the treatment and then decreased over the course of the study. These anomalous results remain unexplained. Costs Basic operating and equipment capital costs were provided by the vendor and estimates were made concerning the frac- tion of feed soil that would be returned to the site as washed soil (assuming clean- up levels are met), that which would be woody debris requiring off-site disposal, and the fraction that would be clay/silt fines amenable to slurry biodegradation. Certain other assumptions were made based on experiences during the demon- stration project and certain other cost fac- tors were assumed to be the responsibility of the site owner/operator. The reasoning used in making these estimates or omit- ting a particular cost category are dis- cussed in the report. Costs were first estimated for a 0.25 to 0.5 ton/hr pilot scale system similar to that used in the demonstration but operating for only 2 wk and without the costs related to the SITE evaluation. Assuming lease of all equipment, the cost estimated was $6.50/kg or $6000/ton of soil treated. Mo- bilization and demobilization and lease costs are major contributors to the high cost of such an evaluation. The cost to treat similarly-contaminated soil in an area such as the MacGillis and Gibbs site with an 18.2 metric ton/hr (20 ton/hr) .commercial soil washer coupled with three 100 gpm BATS units operating in parallel and three parallel SBR trains capable of treating 23 gpm of slurry was estimated at about $168/ton of soil. Dis- posal of the contaminated woody material segregated during soil washing accounts for the major portion (76%) of this cost. Applicability to Other Sites Based on the demonstration and other information provided by the vendor, the BSWS appears to be attractive for soils where: (1) there is a small fraction of fines, (2) the fines retain the bulk of the contaminants, and (3) the fines can be Table 3. PAH Removals in the Slurry Bio-Reactor PAH Acenaphthene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(b)ftuoranthene Benzo(a)pyrene Avg. Cone.' On Influent Solid ' mg/kg 53 + 44 277 + 144 363 + 121 63+.41 89 + 47 69 + 36 48 + 41 Max. % 89 99 94 87 93 75 80 Removal Day of Test 7 14 14 14 14 14 6 On Day 14 % 75 99 94 87 93 75 71 'Includes measured and estimated values in averages. 4 ------- segregated from the bulk of the soil by the BSW process. If the soil contains exces- sive fines (over about 25%), the benefits of soil segregation by particle size begin to become less evident. Water soluble contaminants such as penta tend to dissolve in the aqueous process stream and subsequently can be treated biologically in the BATS. Water- insoluble contaminants such as PAHs (as well as adsorbed penta) can be removed from the slurry of fines by biodegradation, as in the SBR, or can be disposed of by conventional means such as incineration. While no experimental work was done to evaluate such options, it may be fea- sible to customize the system for removal of other contaminants, such as by adding surfactants, adjusting pH, or adding sol- vents. Conclusions For properly selected soils, the BSWS can segregate a large fraction of relatively uncontaminated washed soil. Whether this soil can be returned to the site after de- watering with no further treatment will be dependent on cleanup requirements; this will have a major impact on the cost- effectiveness of the process. Soil character, moisture content, par- ticle size distribution, and contaminant con- centrations and solubilities all are factors in the efficiency and the operability of the soil washer. For example, the soil washer is most effective when the soil contains 25% or less of fine material such as clay and silt. Based on the decrease in contaminants in the washed soil relative to the feed soil, contaminant removal efficiencies of just under the vendor's claimed 90% can be achieved by the soil washing process for penta, PAHs, and even dioxins. Subsequent biotreatment of contami- nated soil washer process water in the BATS can achieve over 90% degradation of penta. Degradation of PAHs could not be determined in this study. The small fraction of fines, even con- taining very high levels of adsorbed penta, can be subjected to biodegradation in the SBR if adequate acclimation time is al- lowed. Significant removal of various PAHs is also achieved in the SBR, but to a much more variable level. For maximum cost-effectiveness, the treated fines should then meet regulatory cleanup requirements and be suitable for return to the site. The cost to treat 1 ton of feed soil in a 20 ton/hr soil washer, combined with the cost to biodegrade the contaminated fines and associated process water before it is recycled and to incinerate woody debris, is approximately $168/ton. Incineration of woody material is the major cost factor. •&U.S. GOVERNMENT PRINTING OFFICE: 1992 - 648-080/40194 ------- ------- ------- The EPA Project Manager, Mary K. Stinson, is with the Risk Reduction Engineering Laboratory, Edison, NJ 08837 (see below) The complete report, entitled "Technology Evaluation Report: BioTrol Soil Washing System for Treatment of a Wood Preserving Site," consists of two volumes: "Volume /" (Order No. PB92-115 310-V1; Cost: $35.00, subject to change) discusses the results of the six-week field demonstration. "Volume II", Part A (Order No. PB92-115 328-V2-Pt A; Cost: $43.00, subject to change) and Part B (Order No. PB92-115 336-V2-Pt B; Cost: $43.00, subject to change) contains the technical operating data - laboratory analytical results, etc. Both volumes of this report will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 A related report, entitled "Applications Analysis Report: BioTrol Soil Washing System for Treatment of a Wood Preserving Site," discusses the applica- tions of the demonstrated technology. The EPA Project Manager can be contacted at: Risk Reduction Engineering Laboratory U.S. Environmental Protection Agency Edison, NJ 08837 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 BULK RATE POSTAGES FEES PAID EPA PERMIT NO. G-35 Official Business Penally for Private Use $300 EPA/540/S5-91/003 ------- |