Sylvain Loranger

Manganese and lead concentrations in ambient air and emission rates from unleaded and leaded gasoline between 1981 and 1992 in Canada: A comparative study

Abstract Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used as an additive in unleaded gasoline. Its use in Canada has increased since 1976 until it completely replaced lead (Pb) in gasoline in 1990. Canada is the only country in the world to have authorized the replacement of Pb in gasoline by MMT. The aim of this study is to compare the concentrations of Mn, Pb and suspended particulates (TSP) in Montreal air from 1981 to 1992, as well as the emission rates of Mn and Pb from mobile sources from the same period. The atmospheric concentrations of Mn, Pb and TSP were measured by the Montreal Urban Community at three sampling stations located in areas of low and high traffic density. The data on emission rates were obtained from Environment Canada and from the Canadian Petroleum Products Institute. Multiple regression and non-parametric correlation analysis were used to predict and to compare the evolution of the chosen variables. Discriminant analysis was used to determine the variables which best distinguish low and high traffic density areas. The results indicate stable Mn concentrations between 1981 and 1990 followed by a substantial decrease, in spite of annual increases of about 10% in Mn emissions from the combustion of MMT since 1981. The decrease observed since 1991 is attributed to the closing of a ferromanganese plant near Montreal. The decrease in atmospheric Pb concentrations observed since 1981 corresponds to the decrease of about 30% per year of emissions from mobile sources over the same period. A definitive evaluation of the environmental contamination and exposure due to Mn from MMT will require an improved estimation of the dispersion of particulates near motorways using dispersion models, as well as receptor modeling based on the physicochemical analysis of particulates using electron microscopy.

Occupational and Environmental Exposure of Garage Workers and Taxi Drivers to Airborne Manganese Arising from the Use of Methylcyclopentadienyl Manganese Tricarbonyl in Unleaded Gasoline

Occupational and environmental exposure to airborne manganese has been measured for two groups of workers in Montreal, taxi drivers and garage mechanics. In Canada methylcyclopentadienyl manganese tricarbonyl (MMT) has replaced lead as an anti-knock agent in gasoline and represents a potentially important source of manganese contamination for the population in general and for the two chosen groups of workers in particular. Twenty workers (10 taxi drivers and 10 garage mechanics) wore a personal air sampler for five consecutive working days and two off-work periods. The amount of total Mn on each filter was determined by neutron activation analysis and then converted to atmospheric Mn concentrations. The values obtained varied from 0.004 microgram m-3 to 2.067 micrograms m-3. At work the garage mechanics were exposed to an average of 0.250 microgram m-3 and the taxi drivers to 0.024 microgram m-3. Off-work, the two groups were exposed respectively to an average of 0.007 microgram m-3 and 0.011 microgram m-3. In the garages there was twice as much Mn in the air on days when the doors were closed compared to days when they were left opened (0.314 micrograms m-3/0.152 microgram m-3). The levels found in this study remain well below the established limits for occupational and environmental airborne exposure. These results will lead to further studies to positively identify the source of Mn as MMT and to explore other pathways leading to the contamination of the general population.

Environmental Contamination and Human Exposure to Airborne Total and Respirable Manganese in Montreal

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organometallic compound used as an octane improver in unleaded gasoline. The combustion of MMT leads to the formation of manganese (Mn) oxides, mainly Mn3O4. The objective of this study is to assess the variations over time and space of respirable (MnR) and total (MnT) Mn in the urban atmosphere and to evaluate human exposure by inhalation. Two sampling sites were selected on the island of Montreal based on their local traffic density (municipal botanical garden, C- = 10,000-15,000 vehicles d-1; Montreal Waterworks, C+ = 100,000-130,000 vehicles d-1). Air samplings were made during the day at stations located 10 m from the road using portable pumps, some of which were equipped with a cyclone. MnR and MnT and other metals were measured on Teflon filters by neutron activation. Mn exposure doses by inhalation were calculated using Monte-Carlo simulations. MnR and MnT average concentrations were significantly higher at site C+ (MnR = 0.024 microgram m-3; MnT = 0.050 microgram m-3) than at site C- (MnR = 0.015 microgram m-3; MnT = 0.027 microgram m-3). Temporal profiles at sites C+ and site C- were similar, with a coefficient of correlation of 0.24 for MnR and 0.26 for MnT. Trend analyses (ARIMA) also showed that the period of the week (work days vs. off days) was significantly related to MnR and MnT variations at both sites. The average exposure dose by inhalation to MnR and MnT ranged from 0.001 to 0.030 microgram kg-1 day-1 and 0.001 to 0.05 microgram kg-1 day-1. MnR and MnT concentrations reflected a positive relationship with traffic density. However, it remains difficult to attribute these results directly to the combustion of MMT in unleaded gasoline. On average, the MnR and MnT inhalation doses were 2 to 15 times lower than the reference dose (RfC) proposed by the U.S. Environmental Protection Agency (EPA) for the general population.

Environmental and occupational exposure to manganese: a multimedia assessment

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic additive used in Canada since 1976 as an anti-knock agent in unleaded gasoline. Its combustion leads to the emission of Mn oxides, especially Mn3O4. Since no study has assessed the potential risk of chronic exposure to low concentrations resulting from these emissions, the present investigation was undertaken to assess the level of environmental and occupational exposure of the human population. The multimedia exposure of two groups of workers (garage mechanics and blue-collar workers) potentially exposed to different levels of Mn from the combustion of MMT was assessed using personal air samplers, a dietary compilation, water samples at their places of residence, an epidemiological questionnaire and blood and hair samples. Results show that garage mechanics were exposed on average to higher atmospheric Mn at work (0.42 µg/m3) than the blue-collar workers (0.04 µg/m3). However, the contribution of atmospheric Mn to the total absorbed dose was less than 1%, and well below the standards estabished for occupational or environmental exposure; food contributes more than 95% of the multimedia dose. The average whole blood Mn concentrations were similar for the two groups (0.67–0.76 µg/100 ml) and fall within the normal adult range. The average hair Mn concentrations were significantly higher for the garage mechanics (0.66 µg/g) than for the blue-collar workers (0.39 µg/g). The contribution of exogenous Mn versus endogenous Mn is questioned. As judged by the governmental standards or criteria for occupational and non-occupational environments, the current Mn levels in food, water and air may not cause any problems for the workers.

Manganese contamination in Montreal in relation with traffic density

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese used as an additive in unleaded gasoline in Canada since 1977. Moreover, Canada is the only country in the world to have authorized the replacement of lead alkyls by MMT in gasoline. The purpose of the present study is to assess the importance of air contamination by Mn in relation to other air pollutants (gaseous and particulates), meteorological variables and traffic density. The concentration of both the gaseous (O3, CO, NO, NO2, SO2) and the particulate pollutants (Mn, Pb, NO−3, SO−−4, TSP) had been measured by the Montreal Urban Community in 1990 at seven sampling stations located in high traffic and low traffic density areas. Data on the meteorological conditions during that same period were also used. Non-parametric correlation, ANOVA and discriminant analyses were used to compare gaseous and particulate pollutants found between both levels of traffic density. In almost 50% of the daily air samples measured in 1990, the Mn concentrations are higher than the urban background level estimated at 0.04 μg m−3 and the variations of Mn concentrations are significantly correlated in time with traffic density. Moreover, Mn and TSP discriminate the best high and low traffic density areas. No significant differences have been observed between Pb, O3 and SO2 concentrations in both areas. These results should not be interpreted in terms of potential health effects since it is presently impossible to determine the fate of the Mn in the environment and its importance in terms of human exposure.

The pigeon (Columbia livia) as a monitor for manganese contamination from motor vehicles

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used in unleaded gasoline in Canada since 1977. It has been suggested that the production of Mn3O4 resulting from the combustion of MMT may become one of the principal sources of manganese contamination in the urban environment. This research evaluates the feral pigeon (Columba livia) as a monitor of Mn contamination in rural (Lachute) and urban (Montreal) environments. Atmospheric Mn concentrations were measured over a 6-month period in the rural and urban areas. Twenty pigeons were captured in each area and the Mn concentrations of several tissues (liver, kidney, lung, pancreas, intestine, brain, down feathers, feces, whole blood, and blood serum) were measured by neutron activation. Biochemical profiles of the blood samples (total protein, aspartate aminotransferase, hematocrit, glucose, and uric acid) were also measured. Air particulate data showed significantly higher Mn levels (p<0.05) in the urban area (0.036 μg/m3) relative to the rural area (0.026 μg/m3). Mn concentrations were similar (P>0.05) in the two groups of pigeons for all the tissues except liver (Lachute=2.42 ppm; Montreal=3.13 ppm) and feces (Lachute=32.2 ppm; Montreal=46.8 ppm); the urban pigeons had about 35% more Mn than the rural pigeons. Aspartate aminotransferase (AST) was also significantly different in the two groups. These results show the importance of the entero-hepatic cycle in the homeostasis of Mn in blood and other tissues. Since the excess of Mn in the feces and liver of the urban pigeons relative to the rural pigeons was similar to the excess Mn in urban air over rural air, pigeon feces and liver appear to be good biomarkers of Mn contamination. Although it is premature to associate this excess Mn with the combustion of MMT, these results nevertheless lead us to consider the pigeon as an interesting indicator of the potential risk to the ecosystem and to human health.

Bioaccumulation of manganese by plants: influence of MMT as a gasoline additive

Abstract This study on the bioaccumulation of manganese (Mn) by plants was motivated by the increased use of Methylcyclopentadienyl manganese tricarbonyl (MMT) as a replacement for lead in gasoline. Oats and beans were grown in sandy and organic soils at a control site (E o ) and at two other sites weakly (E + ) and highly exposed (E ++ ) to Mn contamination, potentially from a MMT source. Total Mn, Ca, Mg, Fe, Zn and Al were measured in the soils and in the plants (roots, stems/leaves and fruits). Exchangeable Mn was measured in the soils at the beginning and at the end of the exposure period. The pH of the organic and sandy silty soils were found to be lower outdoors (E + and E ++ ) than in the greenhouse (E o ) and exchangeable Mn was found to be significantly higher in the organic soil at E ++ (1.03–1.36 ppm). Higher Mn accumulation was also found in the fruits and stems of oats grown in the organic and sandy soils at E ++ . This Mn accumulation is often associated with increased Fe and Al in the plant. These results suggest that the addition of MMT to gasoline may result in an increase in exchangeable Mn in organic soils. However, it has not been proven that the source of the increased Mn accumulation is indeed MMT in gasoline.

Manganese and other trace elements in urban snow near an expressway

The Mn contamination arising from the combustion of MMT (methylcyclopentadienyl manganese tricarbonyl) in unleaded gasoline was assessed using snow collected at different distances 15, 25, 125 and 150 m from an expressway (Montreal, Canada) in February 1993. The snow samples were analyzed by atomic absorption and by neutron activation for total Mn, Mg, Cu, V, Al, Zn, Fe, Na, and Ca concentrations in the soluble (<0.4 microm) and particulate fractions. ANOVA with ranked values was performed to compare element concentrations and soluble/particulate ratios among receptor sites and depths. Principal component analysis was used to describe the spatiotemporal variations of the deposition rates and the influence of meteorological factors. The average concentration of all trace elements, except Mg, Cu, and V, decreased significantly (p<0.05) from receptor sites near the road (15-25 m) to those farther away (125-150 m). The deposition rates of all metals and ions, except Cu, were highly positively correlated (tau = 0.5-0.9) with each other and inversely correlated with snowfalls. Wind frequency showed no correlation with deposition rate. The spatial trend was similar for all these elements making it difficult to distinguish Mn arising from the combustion of MMT from that due to other sources, such as road dust. Only the soluble/particulate ratio calculated for Mn seemed higher than that for the other metals, which might be explained by the particle size of Mn from MMT (0.2-0.4 microm). The present study only indicates a direct contamination of the snow by road activities and substantial deposition of trace elements near the roadway; no clear link can be established between motor vehicle emissions and the concentration of Mn in snow.

Occupational and Environmental Exposure of Automobile Mechanics and Nonautomotive Workers to Airborne Manganese Arising from the Combustion of Methylcyclopentadienyl Manganese Tricarbonyl (MMT)

Inhalation exposure to manganese (Mn) was measured for a group of garage mechanics and a control group of nonautomotive workers. The airborne Mn exposure of 35 garage mechanics suspected of being relatively highly exposed to Mn from MMT was measured at the workplace over one-week period. It also was measured for 30 nonautomotive workers at the University of Montreal. The environmental exposure also was measured for the two groups, as was the exposure to three other metals, aluminum (Al), iron (Fe), and zinc (Zn). At work the mechanics were exposed to Mn concentrations varying from 0.010 to 6.673 micrograms m-3 with a mean of 0.45 microgram m-5, while the control group was exposed to concentrations varying from 0.011 to 1.862 microgram m-3 with a mean of 0.04 microgram m-3. The mean environmental exposure for the two groups was similar to the Mn concentrations gathered in Montreal in 1992. Workplace concentrations of Al, Fe, and Zn also were higher for the garage mechanics. The results suggest that less than 10% of the Mn exposure of the garage mechanics was due to MMT. The levels of the metals measured were below the established limits for industrial and even environmental exposure.

Variations of trace element concentrations in red spruce tree rings

The potential of coniferous trees as biological indicators of heavy metal atmospheric pollution was investigated. In 31 municipalities of an industrialized region, samples of wood from the trunks of red spruce (Picea rubens) were taken to determine the spatial distribution of accumulated metals. Using the annual rings, these core samples were divided into 5-yr sections to determine temporal variations. The concentrations of Mg, Al, Ca, Mn, Fe, Cu, and Zn were measured by neutron activation analysis. All metals showed the highest concentrations in the most recent wood and the bark. For the wood older than 5 yr, Mn and Zn are stable with time, Mg and Ca decrease, while Al, Fe, and Cu appear to increase. A statistical analysis showed the municipalities with the highest variations in metal concentrations; it also revealed correlations in the fluctuations of several of the metals. As expected, trees in towns near metal refineries contain higher amounts of Mn, Fe, and Al. Large variations in metal concentrations, due to factors not totally understood, were observed. Thus, red spruce is not a sensitive bio-indicator of atmospheric metal pollution.