United States Environmental Protection Agency Solid Waste Emergency Response (5102W) EPA 542-N-95-005 August 1995 Issue No. 21 xv EPA The Applied Technologies Journal for Superfund Removals & Remedial Actions & RCRA Corrective Actions DELAWARE OIL SPILL BIOREMEDIATION FIELD STUDY By Albert D. Venosa, EPA National Risk Management Research Laboratory Last summer, an important field study was undertaken on the shoreline at Fowler Beach in the Delaware Bay. As part of a carefully designed study, 540 gallons of light crude oil were in- tentionally released onto fifteen repli- cate plots to evaluate bioremediation. The research design overcame the flaws of previous studies reported in the lit- erature that based conclusions on com- parisons between one large nutrient- treated plot and one large control plot. The problem with those experiments is that no replicate plots were established to provide a basis for estimating experi- mental error. The objectives of the Delaware study were to obtain highly credible statistical evidence (1) to determine if bio- remediation with inorganic mineral nutrients and/or microbial inoculation enhanced the removal of crude oil con- taminating mixed sand and gravel beaches; and (2) to compute the rate at which such enhancement takes place. Biodegradative loss of oil from the plots was tracked by GC/MS analysis of oil analytes normalized to hopane, a non-biodegrable compound present in all crude oils. A randomized complete block design was used to assess treat- ment effects. Three treatments were evaluated: a no nutrient control; water soluble nutrients (biostimulation); and water soluble nutrients supplemented with a natural microbial inoculum from the site (bioaugmentation). An REMEDIATION MARKETPLACE See the special insert in this issue of TECH TRENDS for information on the Mid-Atlantic Remediation Mar- ketplace, sponsored by the EPA's Technology Innovation Office and Region 3 and the Pennsylvania De- partment of Environmental Re- sources. unoiled and untreated plot served as a background control for microbiologi- cal characterization and baseline bioas- says. Five replicates (blocks) of each of four plots (20 plots in all) were set up in random fashion so that whatever in- ferences could be ascertained from the data would be applicable to the entire beach, not just die test plots. The experimental design provided the best chance to detect if significant treatment effects existed. Statistically significant differences between treated and untreated plots were observed at weeks 2, 4, 8 and 14 for the alkanes and weeks 8 and 14 for the polycyclic aromatic hydrocarbons (PAHs). First order rate constants for treated plots were significantly different from those of the untreated plots. At no time were any significant differences ob- served between plots treated with nu- trients alone and plots treated with nu- trients and the indigenous inoculum. Notable from the data is the fact that the hydrocarbon biodegradation oc- curred to a significant extent in the un- treated plots. This was attributed to the high levels of background nitrogen measured on the beach from Delaware Bay (upwards of 1 milligram (me) ni- trate-nitrogen per liter intersritiaTpore water continuously over the course of the 14-week study). Had the back- ground nutrient levels been closer to those typical of Prince William Sound beaches (i.e., a thousand-fold less), the slopes of the control plots would likely have been much flatter, thus giving rise to highly significant differences be- tween treated and control plots for both alkanes and PAHs, perhaps as early as two weeks after the release. The latter conclusion is speculative, since such low background nutrient levels were not encountered in Dela- ware. However, the goals of the project were met: bioremediation via nutrient enrichment was demonstrated Oil Spills Bio- remediation Ocean, Estuary, Beaches unequivocally with statistically credible data; computed biodegradation rates were high, with an alkane half-life of approximately two weeks and a PAH half-life of approximately four weeks; and bioaugmentation even with indig- enous organisms does not stimulate further declines in hydrocarbons be- yond simple nutrient addition. Based on the fact that nutrient levels in the area were high enough to sup- port significant biostimulative hydro- carbon decay, the recommendation would be not to encourage active bioremediation activities if an oil spill were to occur along the Delaware Bay shoreline. However, for coastlines hav- ing low natural input levels of nutri- ents, bioremediation should definitely be considered a major cleanup option. The study was conducted under a Clean Water Act, section 311, permit. Section 311 allows the Administrator to approve the intentional discharge of less than 1,000 gallons of oil for re- search programs. In October 1994, the Administrator received an applica- tion from the State of Delaware to in- tentionally discharge 540 gallons of crude oil onto a private beach for a bioremediation study. The proposal was strongly supported by EPA s Of- fice of Research and Development and Region 3, the U.S. Coast Guard, the U.S. National Oceanographic and At- mospheric Agency, the U.S. Depart- ment of Interior and several Delaware environmental groups. After an intra- and interagency review, EPA granted the permit in June 1994. For more information on the study, call Albert D. Venosa at EPA's National Risk Management Research Laboratory at 513- 569-7668. A report will be available in the Fall; to get on the mailing send a FAX. re- quest to Albert Venosa at 513-569-7 105. Recy clad/Recy clab le Printed with Soy/Canola Ink on paper that contains at least 50% recycled fiber ------- United States Environmental Protection Agency Solid Waste Emergency Response (5102W) EPA 542-N-95-005 August 1995 Issue No. 21 vvERA The Applied Technologies Journal for Superfund Removals & Remedial Actions & RCRA Corrective Actions DELAWARE OIL SPILL BIOREMEDIATION FIELD STUDY By Albert D. Venosa, EPA National Risk Management Research Laboratory Last summer, an important field study was undertaken on the shoreline at Fowler Beach in the Delaware Bay. As part of a carefully designed study, 540 gallons of light crude oil were in- tentionally released onto fifteen repli- cate plots to evaluate bioremediation. The research design overcame the flaws of previous studies reported in the lit- erature that based conclusions on com- parisons between one large nutrient- treated plot and one large control plot. The problem with those experiments is that no replicate plots were established to provide a basis for estimating experi- mental error. The objectives of the Delaware study were to obtain highly credible statistical evidence (1) to determine if bio- remediation with inorganic mineral nutrients and/or microbial inoculation enhanced the removal of crude oil con- taminating mixed sand and gravel beaches; and (2) to compute the rate at which such enhancement takes place. Biodegradative loss of oil from the plots was tracked by GC/MS analysis of oil analytes normalized to hopane, a non-biodegrable compound present in all crude oils. A randomized complete block design was used to assess treat- ment effects. Three treatments were evaluated: a no nutrient control; water soluble nutrients (biostimulation); and water soluble nutrients supplemented with a natural microbial inoculum from the site (bioaugmentation). An REMEDIATION MARKETPLACE See the special insert in this issue of TECH TRENDS for information on the Mid-Atlantic Remediation Mar- ketplace* sponsored, by the EPA's Technology Innovation Office and Region $ and the Pennsylvania De- partment of Environmental Re- sources. unoiled and untreated plot served as a background control for microbiologi- cal characterization and baseline bioas- says. Five replicates (blocks) of each of four plots (20 plots in all) were set up in random fashion so that whatever in- ferences could be ascertained from the data would be applicable to the entire beach, not just the test plots. The experimental design provided the best chance to detect if significant treatment effects existed. Statistically significant differences between treated and untreated plots were observed at weeks 2, 4, 8 and 14 for the alkanes and weeks 8 and 14 for the polycyclic aromatic hydrocarbons (PAHs). First order rate constants for treated plots were significantly different from those of the untreated plots. At no time were any significant differences ob- served between plots treated with nu- trients alone and plots treated with nu- trients and the indigenous inoculum. Notable from the data is the fact that the hydrocarbon biodegradation oc- curred to a significant extent in the un- treated plots. This was attributed to the high levels of background nitrogen measured on the beach from Delaware Bay (upwards of 1 milligram (mg) ni- trate-nitrogen per liter interstitialpore water continuously over the course of the 14-week study). Had the back- ground nutrient levels been closer to those typical of Prince William Sound beaches (i.e., a thousand-fold less), the slopes of the control plots would likely have been much flatter, thus giving rise to highly significant differences be- tween treated and control plots for both alkanes and PAHs, perhaps as early as two weeks after the release. The latter conclusion is speculative, since such low background nutrient levels were not encountered in Dela- ware. However, the goals of the project were met: bioremediation via nutrient enrichment was demonstrated Oil Spills Bio- remediation Ocean, Estuary, Beaches unequivocally with statistically credible data; computed biodegradation rates were high, with an alkane half-life of approximately two weeks and a PAH half-life of approximately four weeks; and bioaugmentation even with indig- enous organisms does not stimulate further declines in hydrocarbons be- yond simple nutrient addition. Based on the fact that nutrient levels in the area were high enough to sup- port significant biostimulative hydro- carbon decay, the recommendation would be not to encourage active bioremediation activities if an oil spill were to occur along the Delaware Bay shoreline. However, for coastlines hav- ing low natural input levels of nutri- ents, bioremediation should definitely be considered a major cleanup option. The study was conducted under a Clean Water Act, section 311, permit. Section 311 allows the Administrator to approve the intentional discharge of less than 1,000 gallons of oil for re- search programs. In October 1994, the Administrator received an applica- tion from the State of Delaware to in- tentionally discharge 540 gallons of crude oil onto a private beach for a bioremediation study. The proposal was strongly supported by EPA s Of- fice of Research and Development and Region 3, the U.S. Coast Guard, the U.S. National Oceanographic and At- mospheric Agency, the U.S. Depart- ment of Interior and several Delaware environmental groups. After an intra- and interagency review, EPA granted the permit in June 1994. For more information on the study, call Albert D. Venosa at EPA's National Risk Management Research Laboratory at 513- 569-7668, A report mill be available in the Fall; to get on the mailing, send a FAX re- quest to Albert Venosa at 513-569-7105. Racy clad/Recy clab le Printed with Soy/Canola Ink on paper that contains at least 50% recycled fiber ------- SITE Subjects CONE PENETROMETER MOUNTED SENSORS By Lary Jack, EPA National Exposure Research Laboratory, Las Vegas Fiber optics.Laser In August 1994, the EPA Superfund Innovative Technology Evaluation (SITE) Program com- pleted a field demonstration of cone penetrometer-mounted chemical' sensors. Two of the technologies evaluated were: (1) the Rapid Opti- cal Screening Tool (ROST®) mar- keted by Loral Corporation; and (2) the Site Characterization and Analy- sis Penetrometer System (SCAPS) Laser Induced Fluorescence (LIF) developed by the Army, Navy and Air Force. These technologies were designed to detect fluorescing com- pounds such as petroleum wastes and coal tars with rapid sampling and real-time, relatively low cost analysis of the physical and chemical characteristics of subsurface soil. The inherent advantages of such cone penetrometer sensor systems are the high rate of penetration (speed) and the low level of waste generation. Of particular note, is that much of the data is acquired without stoppage and plotted on continuous logs as the data is ob- tained. The SITE demonstration took place at three sites within EPA Re- gion 7, which were selected because of their varying concentrations of wastes (coal tar and petroleum fuels) and their ranges in soil textures. Both technologies are attachments designed to fit a standard cone pen- etrometer (CP) rig which simulta- neously provides a continuous log of subsurface materials. Two fiber op- tic cables run from the sensor up through the center of the penetrom- eter rods along with the wires com- ing from the load cells in the CP. One fiber optic transmits laser in- duced, monochromatic light from the truck down to the sensor where it passes through a sapphire window on the side of the tool. Since the cone is pushing its way into the earth, the window is in direct con- tact with the soil; and, the light passes through the window into the soil. The light energy excites hydro- carbon compounds and causes them to fluoresce, with the resultant energy passing up to the second fiber optic cable to an analyzer in the truck. This produces a log of the contami- nation while the signal from the stan- dard CP head produces (after transla- tion by software) a similar continuous soil classification log. The SITE demonstration evaluated the effectiveness of these sensor sys- tems in sampling and analyzing the physical and chemical characteristics of each waste site's subsurface soils, by comparing each technology's re- sults to the results obtained using conventional reference methods. The demonstration found that the SCAPS and ROST® technologies produced screening level data for the contami- nation while the standard CP pro- duced screening level soil classifica- tions. Specifically the qualitative as- sessment showed that the strati- graphic and the chemical cross sec- tions of the SCAPS and ROST8, and associated CP sensors, were compa- rable to the reference methods in their ability to map subsurface con- taminant plumes at petroleum fuel and coal tar contamination sites. In most cases, a consistent relationship between the fluorescence data and the reference method data was identified. Increases in contaminant concentra- tions were generally followed by in- creases in measured fluorescence. Data from both technologies identi- fied similar zones of subsurface petro- leum and coal tar contamination at each of the three demonstration sites relative to the reference methods. Both technologies produced continu- ous profiles, while the reference methods took only a few selective samples targeting boundaries and zones of contamination. For the SITE demonstration, both technolo- gies could produce relatively continu- ous data on petroleum or coal tar contaminant distribution over a 30- foot depth in approximately 1.5 hours. (The use of these sensors is restricted to the maximum push depth of the cone penetrometer truck. This depth can be as much as 300 feet, or in the case of the demon- stration, 30 to 70 feet.) Based on the SITE demonstration, these technologies produce screening level data. A powerful aspect of both technologies is that they can be ad- vanced with a standard cone pen- etrometer to provide continuous de- scriptions of the subsurface soil con- currently with the chemical data. The combination of chemical and physical sensors allows investigation and remediation decisions to be made more efficiently onsite and will reduce the number of samples that need to be submitted for costly con- firmatory analyses. The added ben- efit of these sensors functioning with- out requiring physical sampling al- lows them to produce data in subsur- face environments that restrict con- ventional sampling. The ROST ® technology is cur- rently available as a service from the developer. The technology is de- signed to be operated by trained technicians. The SCAPS technology is designed to be operated by trained technicians from the Army Environ- mental Center, Army Corps of Engi- neers, Navy, Air Force and the Wa- terways Experiment Section. The SCAPS technology is not currently available for use by private citizens or corporations, although it is available to State and Federal agencies. The target contaminants are primarily polycyclic aromatic hydrocarbons; and, most often, this technology is applied at petroleum fuel release sites. For more information, call Lary Jack at EPA's National Exposure Research Laboratory at 702-798-2373. Innova- tive Technology Evaluation Reports on ROST6 and SCAPS, as well as the other cone penetrometer systems evaluated in the SITE demonstration should be avail- able by November 1995. ------- November 29-30,1995 The Warwick Hotel Philadelphia, Pennsylvania sponsored by: U.S. EPA, Technology Innovation Office co-sponsors: U.S. EPA, Region III PA Dept. of Environmental Protection Southern States Energy Board The U.S. Environmental Protection Agency Technology Innovation Office is sponsoring this conference to provide specific information on current and projected business opportunities in the Mid-Atlantic Region for innovative environmental technologies at the State and Federal levels and in the private sector. The conference will enable attendees to: / Identify opportunities in the remediation marketplace / Gather information on funding and available assistance / Locate points of contact and establish new business relationships The agenda includes: State and Federal markets Public/private partnership opportunities Prime/subcontractor partnering Funding of technology development Overview of international markets Small business guidance Case studies of industry perspectives Will B£> Our ^ ifu! -Hoi! -Hours! Registration information will be sent to you at the end of September. If you do not receive an announcement brochure at that time, please fax your name, address, fax and phone numbers to SAIC, (215) 628-8916 to receive one. For Additional Information Contact: SAIC (800) 783-3870 ------- SITE Subjects GASIFICATION TREATMENT FOR SOILS By Marta K. Richards, EPA National Risk Management Research Laboratory Texaco, Inc. has developed waste gas- ification as an innovative extension of their conventional fuels gasification technology. The Texaco Gasification Process (TCP) was evaluated by EPA's SITE (Superfund Innovative Technol- ogy Evaluation) Program to determine the applicability of the TCP to treat- ment of a hazardous waste-contami- nated soil. Since the TGP is operating af temperatures above the melring point of the inorganic materials in the feed stream, the solid residuals form a glassy slag, while the TGP converts carbonaceous organic materials into a gas mixture, called syngas, consisting primarily of hydrogen and carbon monoxide. This is accomplished by reaction with a limited amount of oxygen (partial oxidation) in a refrac- tory-lined gasifier at temperatures in excess of 2,200 F and at pressures greater than 250 psig. According to Texaco, these temperatures and pres- sures are sufficient to destroy hydro- carbons and organics in the feed and prevent the formation of undesirable organic by-products associated with other coal/fossil fuel conversion pro- cesses. The TGP produces syngas as a chemical intermediate product which can be used in the production of hy- drocarbons, ammonia, methanol and PAHs.VOCs Gasification Soils other chemicals. Alternatively, the syngas can be combusted directly in a gas turbine to produce electricity. The process works as follows. Waste feed, along with coal, oil and/or coke is ground and mixed with water in a high-solids' concentration slurry (gen- erally 55 to 70% by weight). The wa- ter serves as a reactant, a temperature moderator and a transport medium. Liquid and gas fuels, which can be fed directly to the gasifier, need no pre- treatment but may require water or steam moderators. For the SITE dem- onstration at the Texaco Montebello Research Laboratory in South El Monte, California, the slurry feed con- sisted of coal, water, waste soil from the Purity Oil Sales Superfund Site in Fresno, California, and clean soil. The composite slurry was spiked with heavy metals (lead ana barium) to en- sure that the feed contained sufficient levels of contamination to fail the Tox- icity Characteristic Leaching Proce- dure (TCLP) test. The addition of ap- proximately 6.42 Ibs. per hour of chlo- robenzene, a volatile organic, was fed into the gasifier with the slurry to fa- cilitate the calculation of the Destruc- tion and Removal Efficiency (DRE). In the SITE demonstration, slurry was fed into the gasifier, along with oxygen, through an injector nozzle. The chlorinated species in the feed formed hydrogen chloride in the raw syngas; the hydrogen chloride dis- solved into the scrubber water before being purged from the process. The sulfur in the feed formed hydrogen sul- fide or carbonyl sulfide in the product gas. Commercial acid gas and sulfur removal processes scrubbed these sul- fides from the product gas. The re- sidual ash was recovered as a glassy slag. The DRE for chlorobenzene was greater than 99.99%. The average composition of the combustible dry syngas from the TGP was 37% hydro- gen, 36% carbon monoxide and 21% carbon dioxide. No organic compound, other than methane (55 parts per million) was above 0.1 ppm. On the average, the primary TGP solid product, coarse slag, com- plied withthe TCLP regulatory re- quirement for lead [5 milligrams per li- ter (mg/L)] and the TCLP and Cali- fornia Waste Extraction Test (WET) regulatory requirements for barium (100 mg/L). The coarse slag did not meet the WET standard for lead (5 mg/ L). Volatile heavy metals, such as lead, tend to partition and concentrate in (continued on page 4) NORTH OF THE BORDER VACUUM PYROUYSIS FOR ORGANICS IN SOILS From Environment Canada Environment Canada's Development and Demonstration of Site Remedia- tion (DESRT) Program supported the evaluation of the Pyrovac vacuum py- rolysis process developed by Pyrovac International, Inc. The evaluation was carried out by the Laval Univer- sity in collaboration with Pyrovac, with support from DESRT and the Ministere de 1'Environnement et de la Faune du Quebec at the Le Vidangeur de Montreal Inc. site in Mascouche, Que'bec. The site, previously a sand- quarry, was used from 1969 to 1974 ror the dumping of solid residues, as well as for the incineration of petroleum sludges. Fissured basins containing liq- uids and hydrocarbon sludges were abandoned. Today, hydrocarbon tar slabs can be found in several places on the site whose soil and water have been highly contaminated with hydrocar- bons, polycyclic aromatic hydrocarbons and polychlorinated biphenyls (PCBs). The samples collected at the Mascouche site were chosen so as to represent a va- riety of types of soils (sand, clay, tar slabs) and a variety of contamination concentrations. The objectives of the treatment were to reduce the level of or- Hydrocarbons/^ PAHs, PCBs Vacuum pyrolysis Soils ganic contamination so as to respect the Quebec criteria for soil contamina- tion. Prior to pilot-scale demonstration, laboratory scale batch runs were car- ried out in a vacuum pyrolysis reactor and confirmed the potential of the vacuum pyrolysis concept. The evalu- ation continued with the pilot unit. Petroleum hydrocarbon reductions in milligrams per kilogram were: Clay A, from 290 to 5.0; Clay B, from 150 (continued on page 4) ------- |