United States Environmental Protection Agency National Risk Management Research Laboratory Cincinnati, OH 45268 Research and Development EPA/600/SR-01/056 November 2001 Project Environmental Impacts of the of Orimulsion®: Report to Congress on 1 of the Orimulsion Technology Program C. Andrew Miller, Kevin Dreher, Randall Wentsel, and Royal J. Nadeau Orimulsion1, a bitumen-in-water emul- sion produced in Venezuela, was evalu- ated to provide a better understanding of the potential environmental impacts associated with its use as a fuel. A series of pilot-scale tests were con- ducted at the U.S. Environmental Pro- tection Agency's Environmental Research Center in Research Triangle Park, NC, to provide data on emissions of air pollutants from the combustion of Orimulsion 100 (the original formulation), Orimulsion 400 (a new formulation in- troduced in 1998), and a No. 6 (residual) fuel oil. These results, and results of full-scale tests reported in the techni- cal literature, were evaluated to deter- mine the potential air pollutant emissions and the ability of commer- cially available pollution control tech- nologies to adequately reduce those emissions. Emissions of carbon mon- oxide (CO), oxides of nitrogen (NOX), sulfur dioxide (SO2), sulfur trioxide (SO3), particulate matter (PM), and organic and metal hazardous air pollutants (HAPs) were measured from each of these three fuels to provide a comparison between the "new" fuel (Orimulsion) and a fuel that has been commonly used in the U.S. (No. 6 fuel oil). Results indicate that CO, NOX, and PM emissions are likely to be nearly the same as those from the No. 6 fuel oil, that SO2 emis- 1 Orimulsion is a registered trademark of Bitumenes Orinoco, S.A. sions can increase if the Orimulsion sulfur content is higher than that of the fuel it replaces, that the particles gen- erated by Orimulsion 100 and 400 are likely to be smaller in diameter than those generated by No. 6 fuel oil, and that HAPs are also likely to be similar to those from No. 6 fuel oil. Both the full-scale results found in the literature and the pilot-scale results measured at EPA indicate that conventional air pol- lution control technologies can effec- tively reduce emissions to very low levels, depending upon the type of tech- nology used and the desired emission levels. Because the bitumen in Orimulsion is heavier than water and due to the presence of a surfactant in the fuel, spills of Orimulsion are likely to be more difficult to contain and re- cover than those of heavy fuel oil, es- pecially in fresh water. Additional study is needed before adequate containment and response approaches can be de- veloped. Little, if any, work has been conducted by the fuel producer or the scientific community to address the re- maining spill-related issues. This Project Summary was developed by the National Risk Management Re- search Laboratory's Air Pollution Pre- vention and Control Division, Research Triangle Park, NC, to announce key find- ings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). ------- Purpose and Approach The purpose of the report is to address the request by Congress that the U.S. Environmental Protection Agency (EPA) "provide better scientific data on the quali- ties and characteristics of this product [Orimulsion] and the potential environmen- tal impact of its introduction" into com- merce. To address this request, a team led by EPA's National Risk Management Research Laboratory (NRMRL) con- ducted research to examine the potential environmental impacts associated with the use of Orimulsion as a fuel and prepared the report. The EPA research team in- cluded Office of Research and Develop- ment (ORD) staff from NRMRL, the National Health and Environmental Ef- fects Research Laboratory (NHEERL), the National Center for Environmental As- sessment (NCEA), and from the Office of Solid Waste and Emergency Response (OSWER) staff from the Office of Emer- gency and Remedial Response (OERR). In response to reviews of Orimulsion research needs by an interagency panel and a panel of external technical experts, EPA prepared an Orimulsion Technology Assessment Plan (OTAP) to guide its re- search efforts. The reviewers identified the generation and control of air pollutant emissions and the toxicity of those emis- sions as the key areas of needed re- search. Orimulsion spill response, containment, and recovery, and the eco- logical effects of such spills (particularly in fresh water) were considered to be less critical, and could be addressed as needed by the appropriate party or par- ties. The OTAP outlined a phased ap- proach, with the need for subsequent phases to be determined by any signifi- cant questions identified during preced- ing phases. The report describes the efforts, results, and conclusions of Phase 1 of the OTAP. The key questions addressed by the report are: •[Are the emissions from the combus- tion of Orimulsion significantly differ- ent from those from other fossil fuels, and if so, how? •[Can the emissions from the combus- tion of Orimulsion be adequately con- trolled using existing air pollution control technologies? If not, are there modifications to existing technologies that can be made to adequately con- trol emissions, or are new control technologies required? •Qfe the behavior of Orimulsion during a spill significantly different than that of other fossil fuels, and if so, how? •Oft/hat gaps exist in understanding the behavior of Orimulsion based on the behavior of other fossil fuels and the known properties of Orimulsion? Are these gaps serious with respect to understanding the potential environ- mental impacts, and if so, what re- search should be conducted to address these gaps? To address these questions, ORD staff conducted a thorough literature review, visited several full-scale power plants that used Orimulsion as their primary fuel, con- ducted pilot-scale combustion tests, tested measures of pulmonary toxicity of PM generated by Orimulsion combustion, and carried out an independent review of an assessment of environmental risks asso- ciated with Orimulsion use. The report discusses the methods and results of these efforts and draws conclusions based on those results. Background Orimulsion is a liquid fossil fuel con- sisting of an emulsion of approximately 70% bitumen (a naturally occurring heavy petroleum material) from the Orinoco re- gion of Venezuela, approximately 30% water, and a small amount of surfactant. The fuel consists of small (8-24 urn diam- eter) droplets of bitumen emulsified in water and the surfactant. Orimulsion is produced by Bitumenes Orinoco, S.A. (Bitor), a subsidiary of the Venezuelan national oil company Petroleos de Ven- ezuela, S.A. (PDVSA), and derives its name from the combination of "Orinoco" and "emulsion." In recent years, Orimulsion has been proposed as a fuel to replace either coal or heavy fuel oil in utility power plants throughout the world. Orimulsion is cur- rently being used as the primary fuel at nine power plants in Canada, Denmark, Italy, Japan, and Lithuania, representing 3,866 MW of electric power generating capacity and approximately 7.5 million tons of fuel consumption per year. To date, no plant in the U.S. has used the fuel for other than short-term testing. Air Emissions Available technical literature (24 refer- ences describing air pollutant emissions at 9 full-scale sites and 3 pilot-scale fa- cilities) was reviewed to determine the problems and issues believed to be most important with respect to air pollutant emissions and control and to evaluate the levels of emissions experienced by full-scale systems using Orimulsion. Table 1 summarizes data reported in the litera- ture for Orimulsion and heavy fuel oil. SO2 and PM data are for pollutant con- centrations upstream of any control de- vice. The reports indicated that CO emis- sions could be easily controlled by in- creasing combustion air levels. In general, the conventional techniques used to re- duce NOX emissions from oil combustion (staged combustion, reburning, selective catalytic reduction) were reported to be applicable to Orimulsion. CO and NOX were dependent upon boiler oxygen (O2) and the combustion system design, simi- lar to other fossil fuels. SO2 concentra- tions from Orimulsion [upstream of any flue gas desulfurization (FGD)] were con- sistent with SO2 concentrations from other fuels with similar sulfur contents. The lit- erature reported that conventional FGD systems could remove up to 95% of SO2 generated by the combustion of Orimulsion. This would result in controlled emissions of approximately 125 ppm. Full- scale results demonstrated that electro- static precipitators can be used to control PM emissions to a level similar to those of other fossil fuels. Emissions of HAPs were similar for both Orimulsion and fuel oil. For both fuels, volatile and semivolatile organic com- pounds were found in very low quanti- ties and would not be likely to be near the 10-ton/year level specified in Title III of the Clean Air Act Amendments of 1990. Due to the elevated levels of metals in Orimulsion, metal emissions were higher than organics, with nickel (Ni) and vana- dium (V) being found in the highest con- centrations. Although V is not listed as a HAP under Title III, it is of concern be- cause of its potential for causing acute pulmonary damage when inhaled. Ni con- centrations in Orimulsion flue gas were higher than those from heavy fuel oil, but both iron and zinc concentrations were higher in heavy fuel oil flue gases than in those from Orimulsion. Processes have been designed to allow recovery of Ni and V in Orimulsion. At least two plants are currently sending Orimulsion ash to facilities for recovery of one or both met- als, thereby reducing solid waste streams. Data From EPA Pilot-scale Tests Two formulations of Orimulsion (one commercially available and one discon- tinued) and a No. 6 fuel oil were individu- ally tested in a pilot-scale combustor at EPA's Environmental Research Center to allow direct comparison of emissions. Concentrations of CO, nitrogen oxide (NO), SO2, SO3, and PM were measured, as were concentrations of volatile and semivolatile organic compounds and met- als. Measurements of emissions from the different fuels were compared to deter- mine any differences in the amount or character of emissions. The tests were ------- Table 1. Summary of air pollutant concentrations reported in the literature for Orimulsion and heavy fuel oil. (SO2 and PM values are upstream of any control device.) Pollutant CO N0x S02<3> S03<5) PM<3> PM size Literature Data Orimulsion0' 30-1 00 ppm<2> (4 tests) 80-400 ppm (1 0 tests) 2500 ppm 2-15 ppm (6 tests) 1 60-350 mg/Nm3 (8 tests) 98-100%<10um 80-97% <1 urn Heavy Fuel Oil 30-100 ppm (4 tests) 1 80-420 ppm (6 tests) 1 200 ppm<4> 4-1 2 ppm (2 tests) 100-41 5 mg/Nm3 (4 tests) 75-87% <10um 45-51 %<1 urn 1 Most data reported in the literature are for Orimulsion 100, although there are several data points for Orimulsion 400. 2 Concentrations of all pollutants are as measured and are not corrected to account for differences in O2 concentration. 3 Concentrations are measured upstream of any control device. 4 No SO2 values for fuel oil were reported in the Orimulsion literature. The 1 200 ppm value is calculated based on 2% sulfur in the fuel. SO2 concentrations are strongly dependent upon the amount of sulfur in the fuel. 5 Measured using mini acid condensation sampling (MACS) method. conducted following NRMRL Quality As- surance Level II procedures, which included audits of measurement equipment and reviews of data by outside organizations. EPA's pilot-scale results were similar to those reported in the literature in terms of comparison of Orimulsion to heavy fuel oil, with data showing little difference in CO, NOX, or PM furnace exit concentra- tions, and smaller particles for Orimulsion than for heavy fuel oil. The pilot-scale data differed most from the full-scale data for NOX, but were not unreasonable given the difference in combustor system de- sign. The pilot-scale tests provided fur- ther valuable confirmation of the similarity between Orimulsion and heavy fuel oil, and also generated samples for use in pulmonary toxicity testing. Toxicity Testing NHEERL conducted tests measuring the pulmonary toxicity in laboratory ani- mals of PM generated by the combustion of Orimulsion 100, Orimulsion 400, and No. 6 fuel oil. Laboratory rats were ex- posed by intratracheal instillation of dif- ferent doses of PM from each of the fuels burned in the NRMRL combustion tests, as well as Arizona road dust (ARD) and a saline solution. Five biomarkers of pul- monary toxicity or injury [bronchial alveo- lar fluid (BALF) neutrophil/mL, BALF protein, albumin, lactate dehydrogenase (LDH), and eosinophil/mL] were measured at 24 hours post-exposure. Each sample was ranked according to its lowest ob- served effect level (LOEL) for each of the five biomarkers. The relative toxicity rankings for each biomarker were: BALF protein: No. 6 fuel oil > Orimulsion 400 > Orimulsion 100 > ARD = Saline albumin: No. 6 fuel oil > Orimulsion 100 > Orimulsion 400 > ARD = Saline LDH: Orimulsion 400 > Orimulsion 100 = No. 6 fuel oil =ARD = Saline neutrophil: Orimulsion 100 = Orimulsion 400 = No. 6 fuel oil = ARD > Saline eosinophil: Orimulsion 100 = Orimulsion 400 = No. 6 fuel oil > ARD > Saline The conclusion drawn by the toxicity tests is that, under the combustion condi- tions employed in these studies, both Orimulsion formulations generated PM emissions that were capable of produc- ing significant adverse acute pulmonary toxicity. In addition, PM derived from the combustion of Orimulsion 100 and Orimulsion 400 was found to be very simi- lar to No. 6 fuel oil fly ash particles in its ability to induce acute pulmonary toxicity. Different results are possible for PM from full-scale units with different operating conditions, for animals exposed via direct inhalation rather than instillation, or for health-compromised animals. Spills Orimulsion is considered to be a "non- floating" oil and is classified as a "non- petroleum oil" by EPA's Office of Solid Waste and Emergency Response. Once spilled, the bitumen fraction of Orimulsion is likely to either sink or remain neutrally buoyant, rather than forming a coherent surface slick. Special equipment is re- quired to effectively contain and recover Orimulsion spills in saltwater environ- ments, and such equipment is currently used at shipping terminals where Orimulsion is off-loaded. Data gaps remain in understanding the behavior and fate of Orimulsion spilled in fresh water. However, as noted in the OTAP, if Bitor does begin to develop U.S. customers at a site accessible only by fresh water, at a site near bodies of fresh water, or at a site where fresh water can be contaminated by a spill, even indi- rectly, Bitor should be responsible for the research to address the data gaps as they have done for marine environments. Such research does not fall under the Congressional directive for this report and should not be considered to be EPA's re- sponsibility under that directive. However, since EPA is responsible for responding to spills in certain situations, the Agency should continue to investigate Orimulsion spill behavior and response as appropri- ate. EPA, in collaboration with the U.S. Coast Guard, has requested the National Academy of Sciences (NAS) to conduct a study on Orimulsion to evaluate what ad- ditional information is required to effec- tively respond to freshwater spills. EPA is currently conducting smaller studies on Orimulsion characteristics and on spill behavior modeling and will address the data gaps identified by the NAS, as ap- propriate. EPA should remain aware of any research conducted by others regard- ing freshwater spills. ------- Risk Assessment The potential ecological risk associated with the use of Orimulsion was evaluated by a panel of independent reviewers cho- sen by EPA, who examined the detailed work carried out by Bitor to estimate the ecological risk associated with a poten- tial spill in the Tampa Bay, FL, marine environment. The Bitor study compared a hypothetical spill of Orimulsion 100 to a hypothetical spill of an equal volume of heavy fuel oil. The comparative assess- ment examined transport and fate of both fuels, including potential effects on shore- lines and aquatic biota under a range of different spill locations, seasonal varia- tions, and wind and current conditions. The independent reviewers agreed with the major conclusion of the Bitor study that a spill of Orimulsion 100 likely poses a similar or lower risk to Tampa Bay biota than does an equivalent spill volume of No. 6 fuel oil. However, the reviewers noted that parts of the assessment, such as risk characterization, population mod- eling, and impacts to benthic communi- ties, were identified as assessment topics that could be improved. The reviewers felt that these improvements would en- hance the Tampa Bay report, but did not feel that the improvements would impact the report's conclusions. A study of cancer risk associated with air emissions from the combustion of heavy fuel oil in electric utility steam generating units was used as the basis for comparing cancer risks due to the use of Orimulsion with those from the use of heavy fuel oil. The original study evaluated the risk to human health associated with exposure to HAP emissions from electric utility steam generating units and estimated that 0.4 additional incidences of cancer would be caused by exposure to Ni emissions from all 137 oil-fired plants in the U.S. This value was considered to be a conservative esti- mate of the potential cancer risk associ- ated with the use of Orimulsion, based on the Ni emissions from both fuels. Potential Use of Orimulsion Orimulsion can be used in applications similar to coal or heavy fuel oil. Orimulsion is readily used in plants designed to use heavy fuel oil, due to the fuels' similar handling and use characteristics, al- though substantial changes to fuel stor- age and handling equipment, air pollution control systems, and boiler internal com- ponents may be required. The difference in fuel prices between fuel oil and coal may also favor fuel oil as being more likely to be replaced with Orimulsion. The states with the highest fuel oil use are (in order of amount used) Florida, New York, Massachusetts, Connecticut, and Hawaii, all of which are oil consumers and not oil producers. They are also located on the coast and may be more suitable markets for Orimulsion than states with high coal consumption. Conclusions of the Report •[Orimulsion is physically and chemi- cally an emulsified heavy fuel oil with elevated sulfur, V, and Ni content. •[Emissions of air pollutants from Orimulsion are not significantly dif- ferent in character from those from other fossil fuels. Orimulsion will, in general, emit more pollutants than natural gas, about the same as heavy fuel oil, and less than pulverized coal. These comparisons do not hold for all cases and are based on emission levels without air pollution control systems. •[Results from both full- and pilot-scale tests indicate that emissions from the combustion of Orimulsion can be ad- equately controlled using commer- cially available air pollution control technologies. •[Conversion of a plant to use Orimulsion may require significant changes to fuel supply and handling and air pol- lution control equipment and modifi- cations to boiler internal components. •Qn general, Orimulsion generated PM emissions that were capable of pro- ducing significant adverse acute pul- monary toxicity, very similar to the No. 6 fuel oil tested. In all cases, PM from both Orimulsion formulations and the No. 6 fuel oil showed mea- sures of toxicity greater than or equal to either ARD or saline solution. •CThe behavior of Orimulsion in a spill is significantly different than that of most other fossil fuels. •CA review by an EPA-chosen expert panel of a Bitor-funded ecological risk assessment of a potential spill in the Tampa Bay, FL, marine environment agreed with the assessment's con- clusion that a spill of Orimulsion 100 likely poses a similar or lower risk to Tampa Bay biota than does an equiva- lent spill volume of No. 6 fuel oil. •CThe most likely use of Orimulsion in the U.S. in the short term is as a replacement for heavy fuel oil, due to similarity in handling and combus- tion properties, the price differential between the two fuels, and the readi- ness of plants using heavy fuel oil to accept tanker shipments of Orimulsion. These factors would in- dicate that Orimulsion is most likely to be used along the Atlantic and Gulf coasts in the U.S. • The major gaps in understanding Orimulsion behavior are in freshwa- ter spill response and effects. Further work in this area should primarily be the responsibility of the fuel's suppli- ers and users and should not be con- sidered as part of the Congressional directive to provide improved scien- tific information on the environmental impacts of Orimulsion use. EPA should continue to evaluate spill ef- fects, behavior, and response, as appropriate, in support of their legis- lated responsibility for spill response. Recommendations of the Report The following recommendations are made with regard to Orimulsion behavior, its potential environmental impacts, and EPA's role in further studies: 1. Based on the results of Phase 1 of the OTAP, it is not necessary for EPA to proceed with Phases 2 and 3. 2. From the perspective of air pollutant formation and control, Orimulsion should be considered to be a heavy fuel oil, albeit with some properties that require special attention. 3. Studies of Orimulsion behavior in freshwater spills are needed in the event that Orimulsion is transported along fresh waterways or used in situ- ations where spills can reach fresh water, even indirectly. This research should evaluate the behavior and ef- fects of Orimulsion under different conditions (water density, presence of silt or other solids, energy level of waves) and should evaluate means of containing and responding to spills. Bitor or the end user should be re- sponsible for the cost of any such work that directly supports efforts to market Orimulsion in the U.S. EPA should continue to follow any work conducted by others on the behavior and fate of Orimulsion spills and should conduct the research neces- sary to support their legislated re- sponsibility for spill response, outside the scope of the Congressional di- rective to provide improved scientific information on the environmental im- pacts of Orimulsion use. 4. Research recommended in a review by an EPA-chosen panel of a Bitor- funded ecological risk assessment of a potential spill in the Tampa Bay, FL, marine environment is consid- ered to be the responsibility of Bitor. ------- The EPA authors are C. Andrew Miller (also the EPA Project Officer, see below), Kevin Dreher, National Health and Environmental Effects Re- search Laboratory, Research Triangle Park, NC 27711; Randall Wentsel, National Center for Environmental Assessment, Washington, DC 20460; and Royal J. Nadeau, Environmental Response Team, Edison, NJ 08837. The complete report, entitled "Environmental Impacts of the Use of Orimulsion®; Report to Congress on Phase 1 of the Orimulsion Technology Assessment Program; Volume 1: Executive Summary, Report, and Appen- dix A," and "Volume 2: Appendices B-H," will be available at http:// www.epa.gov/ORD/NRMRL/Pubs or from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: (703) 605-6000 (800) 553-6847 (U.S. only) as • Volume 1: Order No. PB2002-109039; Cost: $44.00, subject to change, and • Volume 2: Order No. PB2002-109040; Cost: $44.00, subject to change. The EPA Project Officer can be contacted at: Air Pollution Prevention and Control Division National Risk Management Research Laboratory U. S. Environmental Protection Agency Research Triangle Park, NC 27711 United StatesD Environmental Protection Agency D CenterforEnvironmental Research InformationD Cincinnati, OH 45268D PRESORTED STANDARDD POSTAGES FEES PAIDD EPAD PERMIT No. G-35D Official Business Penalty for Private Use $300 EPA/600/SR-01/056 ------- |