Modeling the environmental fate of manganese from methylcyclopentadienyl manganese tricarbonyl in urban landscapes

Abstract

The environmental impacts of gasoline additives such as lead (Pb) and Methyl Tertiary Butyl Ether (MTBE) are well documented, leading to the phasing out of these additives. In contrast, little is known about the health and environmental impacts of potential replacement chemicals such as Methylcyclopentadienyl Manganese Tricarbonyl (MMT). The combustion of MMT in gasoline leads to the formation of MnPO4 and MnSO4 and MMT is considered a recent source of inorganic Mn in urban landscapes particularly in high traffic areas. The main objective of this study is to estimate the automotive deposition of Mn from MMT relative to the traffic volume at sites near a major highway in the Greater Toronto Area of Canada, where MMT is currently being used. Manganese emission levels were estimated for two sites that varied according to Annual Average Daily Traffic (AADT) density, fuel consumption, distance traveled by automobiles, and Mn concentration (mg l(-1)) in gasoline. Multiple regression analysis was used to predict the AADT volume from year 2002-2010. Comparison of the mass balance between the ANOVA means of 15% Mn emitted from the automobile tailpipes at 10, and 18 mg of Mn l(-1) in gasoline was conducted for both study sites. The percentage difference between the Mn input at the selected concentrations of Mn in gasoline and output into surface soil were found to be 99% significant for both sites. Thus the predicted 15% tailpipe emission levels for 10 mg of Mn l(-1) of gasoline used in automobiles, which represented 1290.03 g/year for site 1 and 555.94 g/year for site 2, will add 5.73 and 2.47 mg/kg of Mn annually, respectively. These input levels are considered negligible when compared to the natural abundance of Mn in soil. Based on these data, it could take more than 95-256 years of continuous MMT usage in the region to double the content of Mn in surface soils at the respective sites.