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Common Myths and Misconceptions About the Behavior and Impact of MTBE Released from Petroleum Products

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Common Myths and Misconceptions About the Behavior and Impact of MTBE Released from Petroleum Products Transactions on Ecology and the Environment vol 65, © 2003 WIT Press, www.witpress.com, ISSN 1743-3541 Common myths and misconceptions about the behavior and impact of MTBE released from petroleum products R. E. woodward' & R. L. sloan2 '~ievvaEnvironmental Services, Inc., Houston, TX 2 Lyondell Chemical Company, Channelview, TX Abstract Auto fuel regulatory-mandates, to decrease the aromatic content of fuels and to reduce exhaust emissions, have led to the expanded use of additives to oxygenate auto fuels in the European Union (EU) and United States (US). The economical ether oxygenates, methyl tertiary butyl ether (MTBE) or ethyl tertiary butyl ether (ETBE) are frequently the oxygenate of choice because they deliver oxygen without increasing the Reid Vapor Pressure (RVP) or altering the fungible characteristics of autofuel. However, transport of auto fuels by common carriers that also transport heating oil and other heavier petroleum products has lead to the discovery of trace concentrations of auto fuel in many petroleum products. Subsequent leaks and spills during storage and handling of petroleum products result in the release of Auto fuel constituents to the environment. Critical review of 12 myths and misconceptions about MTBE in auto fuels reveals the concepts were conceived to rationalize early field observations andlor incomplete data sets. Closer scrutiny, in light of recent laboratory investigations, field data, case studies and world literature, indicates the myths are unsubstantiated misconceptions and assumptions about the behavior of ether oxygenates in the environment. Commonly held myths focus on four general areas of fuel and fuel oxygenates management: storageldispensing, hydrology, remediation, and health effects. Storageldispensing misconceptions address materials stability to ethers in fuel and the environmental forensics of fuel systems failure. Groundwater and hydrology myths deal with plume dynamics and the impact of fuel on drinking water resources. Remediation myths focus on the performance of traditional hydrocarbon remediation technologies, recent developments in biodegradation and natural attenuation, drivers of remedial design and remediation costs. Health effects myths address both acute and chronic exposure risk evaluations by national and international health agencies. MTBE is manageable by the same processes and precautions used for gasoline and other fuel hydrocarbons. Transactions on Ecology and the Environment vol 65, © 2003 WIT Press, www.witpress.com, ISSN 1743-3541 220 Water Pollution \//I: Modclling, Mca~uringand Prediction Introduction h an attempt to rationalize early field observations andlor incomplete data sets, numerous myths and misconceptions have evolve about the fuel oxygenate, MTBE. Invariably, good science has effectively debunked them leading to balanced publication of the issues [l]. This paper explores the basis of 12 myths and provides current interpretations, explanations and supporting data. 1 MTBE degrades storage1handIing facilities It has been claimed that ethers, and specifically MTBE, can prematurely degrade gaskets, seals, hoses, fittings, and valves on gasoline storage and handling facilities. MTBE has been an important component of unleaded gasoline and subsequently reformulated gasolines (RFG) for more than 20 years. MTBE containing formulations have been successfully shipped worldwide in a variety of truck transports, pipelines, and rail transfer facilities. Historically, the materials of these gasoline-handling facilities have been compatible with MTBE and have tested tight. Several detailed reviews over the last three years have not revealed any specific instances where MTBE in gasoline caused premature failure of systems components or resulted in material incompatibility [2]. When the specific systems components were reviewed, it was concluded that the properties of the components were consistent with handling MTBE. During the early use of RFG, the US Coast Guard conducted a study of marine fueling facilities due to concerns about the integrity of specific fuel components and concluded that MTBE did not negatively impact the components marine fueling facilities [3]. 2 MTBE alone leaks from gasoline tanks When an underground fuel storage tank fails, all of the chemical components of the fuel are released into the subsurface soils and likely into the underlying groundwater. Typically, gasoline may contain 6% MTBE by volume, which means that 94% of what leaks into the soil and groundwater is other gasoline components by volume. When a leak occurs, the MTBE in the gasoline is a small percentage of the hydrocarbon released to the environment. In comparison, aromatic hydrocarbons like benzene and its derivatives comprise up to 34% v/v gasoline. The media has frequently reported that MTBE leaked from a gasoline tank or that a railcar containing gasoline, leaked and MTBE spilled onto the ground or into surface water. This is very misleading since it implies that only MTBE was released to the environment. In reality over 200 chemical components of gasoline were released to the environment [4]. Indeed, many of these chemicals pose a much greater risk to the public health and the environment than does MTBE. Transactions on Ecology and the Environment vol 65, © 2003 WIT Press, www.witpress.com, ISSN 1743-3541 3 MTBE travels far beyond BTEX plumes When gasoline chemical components, including MTBE, contact groundwater, these chemicals will dissolve, based on their respective solubility limits and site-specific conditions. The chemicals will then migrate with the groundwater. Dissolved chemicals cannot travel faster than the groundwater but they may travel slower if their movement is retarded by adsorption to the soil. The physical behavior of two components of gasoline, MTBE and Benzene, is compared and contrasted graphically in Figure 1. Several processes occur when groundwater plumes migrate; the chemicals in the water are diluted and dispersed; the chemicals may adsorb onto the soil particles or desorb from soil particles; the chemicals may aerobically or anaerobically biodegrade. Figure 1. Relative Physical Characteristics and Behavior of MTBE and Benzene. The net result is that MTBE will tend to exist on the leading edge of a typical groundwater plume; however the other gasoline components, e.g. BTEX, will tend to exist immediately behind the leading edge of the plume [5]. Historically, accurate interpretation of plume position and composition has been complicated by analytical detection limits for BTEX. Frequently, laboratories report MTBE but not BTEX, even though chromatographic peaks for aromatics are clear. Review of the data often reveals BTEX, at some concentration, immediately behind the leading edge of Transactions on Ecology and the Environment vol 65, © 2003 WIT Press, www.witpress.com, ISSN 1743-3541 222 Water Pollution \//I: Modclling, Mca~uringand Prediction the plume. Several recent studies of groundwater plumes associated with gasoline releases have confirmed that MTBE and BTEX plumes frequently coincide [6]. 4 MTBE plumes sink (or dive) Behavior of free-phase hydrocarbons in groundwater is a function of their density. MTBE and the other components of gasoline have a specific gravity less than 1. Consequently free-phase gasoline, with MTBE or without, floats on the groundwater water table. When the components of gasoline dissolve into the groundwater, they move with it through the aquifer. The addition of new water to an aquifer is called recharge. If recharge occurs from the surface, older aquifer water and its dissolved constituents may be pushed downward in the formation. Likewise, pumping of an aquifer at depth may pull the water table and constituents dissolved in the groundwater to deeper locations in the formation. In any event, dissolved constituents follow groundwater flow. For this reason it is important to conduct complete, three-dimensional characterization of plumes prior to remedial action [7]. 5 MTBE is a threat to drinking water resources Any chemicals, metals or other toxic substances are a potential threat to drinking water supplies if they are released in a potential drinking water recharge area. The actual .threat is based on the properties of the specific chemicals, metals, etc. and on the concentration of those constituents. California Public Water Supply Wells (PWSW) impacted by MTBE, and indeed the overall number of Leaking Underground Fuel Tanks (LUFTs), have decreased since 1995 (Table 1)[8]. PWSW were sampled at three intervals during the period from 1995 to 2001 and the number of MTBE detections noted. During that period the percentage of MTBE detections decreased Erom 1.20% to 0.60% of the sampled wells. This downward trend continues, due in part to improved monitoring, tank and distribution upgrades and rapid responses to releases of gasoline. Table 1. MTBE detection in California PWSW 1995-2001 bime Interval 1 95-98 1 98-99 1 99-01 / PWSW Sampled during period 2988 1567 3426 Total PWS Sampled 2988 4555 798 1 Total PWSW with MTBE detects 34 41 46 % PWSW with MTBE detects 1.20% 0.90% 0.60% Source: California Department of Health Services [8]. At concentrations found in groundwater near leaking underground tanks or spills, MTBE is not toxic to human beings, but its associated taste threshold may trigger Transactions on Ecology and the Environment vol 65, © 2003 WIT Press, www.witpress.com, ISSN 1743-3541 avoidance [g]. The presence of MTBE in spilled or leaked gasoline does not increase the treat that the gasoline
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