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A Physical–chemical Screening Model

A Physical–chemical Screening Model

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Published by api-3861299
A physical–chemical screening model for
\
anticipating widespread contamination of community
\
water supply wells by gasoline constituents
A physical–chemical screening model for
\
anticipating widespread contamination of community
\
water supply wells by gasoline constituents

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Published by: api-3861299 on Oct 19, 2008
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05/09/2014

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A physical\u2013chemical screening model for
anticipating widespread contamination of community
water supply wells by gasoline constituents
J. Samuel Arey, Philip M. Gschwend*
Ralph M. Parsons Laboratory, 48-413, Department of Civil and Environmental Engineering,
Massachusetts Institute of Technology, Cambridge, MA 02139, United States
Received 6 August 2003; received in revised form 9 August 2004; accepted 17 August 2004
Abstract

Continuing modifications of fuels like gasoline should include evaluations of the proposed constituents for their potential to damage environmental resources such as subsurface water supplies. Consequently, we developed a screening model to estimate well water concentrations and transport times for gasoline components migrating from underground fuel tank (UFT) releases to typical at-risk community water supply wells. Representative fuel release volumes and hydrogeologic characteristics were used to parameterize the transport calculation. Subsurface degradation processes were neglected in the model in order to make risk-conservative assessments. The model was tailored to individual compounds based on their abundances in gasoline, gasoline\u2013water partition coefficients (Kgw), and organic matter\u2013water partition coefficients (Kom). Transport calculations were conducted for 20 polar and 4 nonpolar compounds found in gasoline, including methyltert-butyl ether (MTBE) and other ether oxygenates, ethanol, methanol, and some aromatic hydrocarbons. With no calibration, the screening model successfully captured the reported magnitude of MTBE contamination of at-risk community supply wells. Such screening indicates that other oxygenates would cause similar widespread problems unless they were biodegradable. Stochastic analysis of field parameter variability concluded that community supply well contamination estimates had order-of- magnitude reliability. This indicated that such pre-manufacturing analyses may reasonably

0169-7722/$ - see front matterD 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2004.08.002
* Corresponding author. Tel.: +1 617 253 1638.
E-mail address:pmgschwe@mit.edu (P.M. Gschwend).
Journal of Contaminant Hydrology 76 (2005) 109 \u2013 138www.elsevier.com/locate/jconhyd
anticipate widespread environmental problems and/or inspire focused investigations into chemical
properties (e.g., biodegradability) before industrial adoption of new fuel formulations.
D2004 Elsevier B.V. All rights reserved.
Keywords:MTBE; BTEX; Screening model; Community water supply well; Gasoline additive; Subsurface
transport; Partition coefficient; Monte Carlo
1. Introduction
1.1. Motivation

Less than 10 years after the widely increased addition of methyltert-butyl ether (MTBE) to U.S. gasolines, widespread contamination of thousands of drinking water supply wells caused enormous environmental and economic costs (Squillace et al., 1996;

Johnson et al., 2000). Due to its abundance in gasoline, high aqueous solubility, and slow

degradation rate in aquifers, MTBE has migrated in significant quantities from subsurface gasoline releases to many municipal and private water wells across the U.S. in only a few years (Squillace et al., 1997). Although the U.S. Environmental Protection Agency (EPA) mandated oxygenated fuel use in many regions in 1990 (Davis et al., 1998), some investigators had used qualitative language to warn about the potential threat of MTBE to groundwater resources as early as 1986 (Garrett et al., 1986; Page, 1989). Despite such early warnings and subsequent experiences with MTBE, an approach for making an a priori quantitative evaluation of widespread water supply well contamination from underground fuel tank (UFT) related releases or other sources has not yet been developed. These events demonstrate the clear need for regulators and industry to pre-evaluate all future gasoline additives and/or adjust gasoline composition for the corresponding potential to contaminate subsurface water supplies.

Extensive surveys of U.S. water supplies over the last decade have consistently
reported a high incidence of community supply well contamination at levels of ~1 to 20
Ag/L MTBE. According to a U.S. EPA collection of reports, in high oxygenate use areas, 5

to 15% of community drinking water supply wells had MTBE concentrations ofz0.1Ag/ L, and about 1% had MTBE concentrations in the range of 5 to 20Ag/L or higher (Greenbaum et al., 1999). In a more systematic national sampling program of 579 community supply wells by the U.S. Geological Survey (USGS), the survey sample was designed to reflect a random national distribution of well sizes and population density, finding 5.4% of wells to havez0.2Ag/L MTBE concentrations, all less than 20Ag/L (Grady, 2002). In a study of the northeastern states, where oxygenate use is more common, workers used a similarlybstratifiedQ sampling strategy and found 7.8% of community supply wells to have MTBE levels ofz1.0Ag/L (Grady and Casey, 2001). MTBE concentrations as high as 610Ag/L were reported in Santa Monica community supply wells as a result of contamination from nearby leaking underground fuel tanks (LUFTs) (Brown et al., 1997). MTBE contamination of public or private drinking water wells appears to result largely from UFT and local homeowner fuel releases or refueling spills (Johnson et al., 2000). It is worth noting that non-point source transport of MTBE from the

J.S. Arey, P.M. Gschwend / Journal of Contaminant Hydrology 76 (2005) 109\u2013138
110
atmosphere to shallow groundwater in urban areas has also been suggested as a contributor
to pervasive contamination of drinking water supplies at sub-Ag/L concentrations (Pankow
et al., 1997; Baehr et al., 1999; Baehr et al., 2001).

A useful assessment for identifying which gasoline compounds could cause widespread contamination of water supplies must incorporate chemical property information relating to subsurface transport. In principle, any component of gasoline might contaminate drinking water resources as a result of transfer from released gasoline to groundwater, followed by advective (groundwater flow) transport to a public or private well. In practice, most gasoline constituents are sparingly soluble in water, highly sorptive to aquifer solids and therefore retarded with respect to groundwater flow, or substantially biodegraded in the subsurface before migration to drinking water wells. Therefore, to make an upper-bound estimate of the threat posed by gasoline components to water supply wells, one could use a transport model that neglects biodegradation but utilizes information on equilibrium distributions of the contaminants between phases: primarily water, gasoline, air, and aquifer solids (MacFarlane and Mackay, 1998; Schwarzenbach et al., 2003). The corresponding chemical properties are partition coefficients,K12, which quantify the chemical\u2019s equilibrium mass distribution between two phases:

K12\u00bcconcentration of solute in phase 1
concentration of solute in phase 2
\u00f01\u00de

The partition coefficients relevant to subsurface transport of gasoline constituents therefore include the gasoline\u2013water partition coefficient (Kgw), the air\u2013water partition coefficient (Kaw), and the organic matter\u2013water partition coefficient (K om).

In a regulatory context, gasolines are conventionally viewed as mixtures of nonpolar
hydrocarbons and any added oxygenates (EPA, 1987; Hoffer, 1987; Belk et al., 1993;
Gardner and Moore, 1993; Davis et al., 1998). However, closer scrutiny reveals that

gasolines contain a suite of polar constituents at levels between 10 and hundreds of parts- per-million (ppm,Table 1). These compounds are either present in the original petroleum, are byproducts of refining processes, or are intentionally added in order to improve engine performance, clean and lubricate valves, increase octane number, improve emissions quality, preserve fuels during storage, or perform other functions (Owen, 1989). Such compounds could threaten drinking water resources widely if they are sufficiently mobile in the subsurface. As with MTBE, it is useful to consider whether the contamination risk posed by these compounds could be anticipated a priori, in other words, independently of existing contamination data. An analogous screening method for estimating urban air contamination levels by volatile gasoline constituents such as MTBE was proposed recently (Kawamoto et al., 2003).

1.2. Objective

The goal of this study was to develop and test a method for evaluating the plausibility of significant contamination of community supply wells (CSWs) resulting from the use of current or future gasoline additives. For this purpose, we chose to make the conservative assumptions that (a) gasoline constituents were not (bio)degraded in the subsurface, and

J.S. Arey, P.M. Gschwend / Journal of Contaminant Hydrology 76 (2005) 109\u2013138
111

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