Ugwoha, Ejikeme
(2013)
Impact of soil organic matter on groundwater contamination risks for ethanol and butanol blended gasoline.
PhD thesis, University of Nottingham.
Abstract
This work examined the impact of soil organic matter (SOM) on the sorption, phase distribution and transport of ethanol and butanol blended gasoline vapours after release. Microcosm and mini-lysimeter experiments were conducted using sand with varying SOM and moisture contents. Synthetic gasoline alone and blended with 10 - 20% ethanol and 10 - 20% butanol by volume, referred to as UG, E10 - E20 and B10 - B20, respectively, were used. Results from the UG were used as the benchmark to assess the impact of ethanol and butanol on gasoline compounds. The findings of this work illustrate the likely behaviour of gasoline compounds at the beginning times of a gasoline spill or leak.
The addition of alcohol to gasoline altered the behaviour of the gasoline compounds in the vadose zone in several ways. Firstly, it reduced the sorption of the gasoline compounds by soils. This effect was greatest on the first day of a spill and affected the gasoline compounds in decreasing order of hydrophobicity. Secondly, it altered the mass distribution of the gasoline compounds between the vadose zone phases to higher mass compounds in the mobile phases (soil air and soil water) and lower mass compounds in the immobile soil solid phase, suggesting higher risk of groundwater contamination with an increasing content of alcohol in the gasoline. Thirdly, it increased the vapour phase transport of the gasoline compounds from the source zone to the groundwater zone. These three impacts were generally greater for ethanol than butanol. The sorption coefficients (Kd) of E20 gasoline compounds were reduced by 54% for alkanes, 54% for cycloalkanes and 63% for the aromatics, while the Kd of B20 gasoline compounds decreased by 39% for alkanes, 38% for cycloalkanes and 49% for aromatics. This implies that the use of ethanol as gasoline oxygenate could result in greater risk of groundwater contamination with gasoline compounds than the use of butanol after spills.
The SOM enhanced the sorption of alcohol-blended gasoline compounds in soils. This impact was similar for ethanol and butanol blended gasoline as the Kd of B20 and E20 were equally increased by 7 times for aromatics, 4 times for cycloalkanes and 2 times for alkanes, for 0 to 5% increase in the SOM fraction of sand. Although SOM enhanced the sorption of alcohol-blended gasoline, its sorptive capability was not fully realised compared with the sorption of the UG compounds. Also, it did not alter the order of groundwater contamination risk for the ethanol and butanol blended gasoline. Thus, the Kd values for all gasoline compounds for all the SOM fractions tested, including 0%fom, 1%fom, 3%fom and 5%fom, were in the order of UG>B20>E20, indicating greater risk of groundwater contamination for the ethanol-blended gasoline after a spill or leak regardless of the SOM content of the soil.
The increase in the water content of soil reduced the sorptive capability of SOM and affected the overall mass distribution of gasoline compounds between the soil solid, soil air and soil water phases estimated with values of Henry’s law constant from the literature. This indicates that the degree of gasoline retention in the vadose zone by SOM could differ during the dry summer and wet winter seasons. This effect was greater for ethanol than butanol. Thus, in all seasons, the amount of gasoline compounds retained by SOM in the vadose zone is likely to be higher for butanol-blended gasoline than ethanol-blended gasoline.
Overall, this study indicates that the use of high ethanol volume in gasoline to combat climate change may put the groundwater at greater risk of contamination after spills or leakages from storage. Therefore, to successfully reduce greenhouse gases emissions via high alcohol volume in gasoline and still protect the world’s groundwater resource, this study suggests the use of butanol is more benign than ethanol.
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