Oral manganese intake estimated with dietary records and with direct chemical analysis.

The estimation of the daily oral intake of manganese (Mn) can vary significantly with the method used. This study aims to compare two different approaches: the use of dietary records along with tables of the Mn contents of different foods and the parallel collection of identical aliquots which are analyzed for Mn. Dietary samples and information were collected during a 3-day dietary assessment with five participants. The average daily oral intake of Mn estimated from the dietary records and tables of Mn contents was 3.52 mg/day (S.D. = 1.9), which corresponds to an exposure dose (ED) of 50.27 microg/kg body wt./day (S.D. = 26.2). With a parallel collection of identical aliquots and chemical analysis, the average intake was 2.88 mg/day (S.D. = 0.64) for an ED of 41.18 microg/kg body wt./day (S.D. = 8.9). Thus, the use of tables gives an estimated oral dose 22% higher than the more accurate direct chemical analysis.

Assessment of bioaccumulation and neurotoxicity in rats with portacaval anastomosis and exposed to manganese phosphate: a pilot study.

The use of the additive methylcyclopentadienyl manganese tricarbonyl in unleaded gasoline has resulted in increased attention to the potential toxic effects of manganese (Mn). Hypothetically, people with chronic liver disease may be more sensitive to the adverse neurotoxic effects of Mn. In this work, bioaccumulation of Mn, as well as histopathology and neurobehavioral damage, in end-to-side portacaval anastomosis (PCA) rats exposed to Mn phosphate via inhalation was investigated. During the week before the PCA operation, 4 wk after the PCA operation, and at the end of exposure, the rats were subjected to a locomotor evaluation (day-night activities) using a computerized autotrack system. Then a group of 6 PCA rats (EXP) was exposed to 3050 microg m(-3) (Mn phosphate) for 8 h/day, 5 days/wk for 4 consecutive weeks and compared to a control group (CON), 7 PCA rats exposed to 0.03 microg m(-3). After exposure, the rats were euthanized and Mn content in tissues and organs was determined by neutron activation analysis. The manganese concentrations in blood (0.05 microg/g vs. 0.02 microg/g), lung (1.32 microg/g vs. 0.24 microg/g), cerebellum (0.85 microg/g vs. 0.64 microg/g), frontal cortex (0.87 microg/g vs. 0.61 microg/g), and globus pallidus (3.56 microg/g vs. 1.33 microg/g) were significantly higher in the exposed group compared to the control group (p <.05). No difference was observed in liver, kidney, testes, and caudate putamen between the two groups. Neuronal cell loss was assessed by neuronal cell counts. The loss of cells in globus pallidus and caudate putamen as well as in frontal cortex was significantly higher (p <.05) for the EXP group. Assessment of the locomotor activities did not reveal any significant difference. This study constitutes a first step toward our understanding of the potential adverse effects of Mn in sensitive populations.

Bioaccumulation and locomotor effect of manganese dust in rats.

The primary goal of this study is to determine the effects of Mn exposure via inhalation. The bioaccumulation of Mn in different organs and tissues, the alteration of biochemical parameters, and the locomotor activity were assessed. A group of 26 male Sprague-Dawley rats (E) were exposed to 3750 microg/m(3) of Mn dust for 6 h/day, 5 days/wk for 13 consecutive weeks and compared to a control group of 12 rats (C) exposed to 4 microg/m(3). After exposure, neurological evaluation was carried out for 36 h (a night-day-night cycle) using a computerized autotrack system. Rats were then sacrificed by exsanguination, and Mn content in organs and tissues was determined by neutron activation analysis. Mn concentrations in lung, putamen, and cerebellum were significantly higher in E than in C (0.30 vs. 0.17, 0.89 vs. 0.44, 0.63 vs. 0.48 ppm; p <.01), as well as in the kidney, frontal cortex, and globus pallidus (1.15 vs. 0.96, 0.84 vs. 0.47, 1.28 vs. 0.55 ppm; p <.05). Potassium concentration was significantly lower in E than in C (5.11 vs. 5.79 mmol/L; p <.05), as was alkaline phosphatase (106.9 vs. 129.6 U/L; p <.01). Locomotor activity indicated higher distance covered in the first 12-h period for E (45 383 vs. 36 098 cm; p <.05) and lower resting time in the last 12-h period for E (36 326 vs. 37 393 s; p <.05). This study is the first of several ongoing studies in our laboratory that address health concerns associated with inhalation exposure to different Mn species and to different levels of exposure.

Use of MMT in Canadian gasoline: health and environment issues.

BACKGROUND: Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used in Canadian gasoline since 1976 as an antiknock agent and to improve octane rating. Combustion products of MMT are mainly a mixture of Mn phosphate and Mn sulfate. In 1997, the Canadian federal government adopted a law (C-29) which banned both the interprovincial trade and the importation for commercial purposes of manganese-based substances, including MMT. However, the government reworded this law in July 1998 so that manganese-based fuel additives were not included in the restrictions. MMT is now approved for use in Argentina, Australia, Bulgaria, the United States, France, Russia, and conditionally in New Zealand. Nevertheless, these countries are not using MMT intensively and they are waiting for strong evidence of the absence of effects on human health. Even after several years of use of MMT in Canada, many uncertainties remain. METHODS: Different methods were used in order to assess (1) environmental contamination and human exposure to the parental form of MMT, (2) nitrogen oxides (NO(x)) and carbon monoxide (CO) emissions associated with the use of MMT, and (3) qualitative and quantitative assessments of Mn emissions to the environment. RESULTS: The results provide timely information with regard to the impact of MMT on environmental/ecosystem Mn contamination in abiotic and biotic systems as well as on human exposure. Moreover, results raise major concerns with regard to public health effects related to exposure to Mn. CONCLUSIONS: Obviously, there is still an important lack of adequate toxicological information and further studies are needed to provide successful implementation of evidence-based risk assessment approaches.

Health effects of residential exposure to aluminum plant air pollution.

In this study, the authors evaluated the relative risk of residential exposure to air pollution from an aluminum plant. The authors used government-compiled data to compare hospital admissions in 1997 for selected respiratory diseases for 2 communities in Brazil. One community, Ouro Preto, was located near an aluminum plant, and the other, Diamantina, was located far from any source of industrial air pollution. The relative risk of hospital admissions for selected respiratory diseases was 4.11 (95% confidence interval = 2.96, 5.70). The risk was highest among individuals between 30 and 39 yr of age (relative risk = 11.70; 95% confidence interval = 1.52, 89.96). Admissions per thousand residents were highest for individuals under 10 yr of age and for individuals older than 70 yr of age. The authors assessed exposure with environmental measurements. Dust deposition was collected in the residences of participants (n = 36 in each location), and the dust was analyzed for aluminum, manganese, magnesium, and calcium content. There were significantly different (p < .05) levels of aluminum in the 2 communities; the highest quantities were found near the aluminum plant. Measurements from independent studies indicated that both 24-hr maximum values and annual mean concentrations of suspended particulate matter exceeded the average of international standards in Ouro Preto (i.e., aluminum plant area). These results suggested that exposure to greater air pollution in the aluminum plant area (i.e., Ouro Preto, Brazil) versus the control area resulted in statistically significant health effects in those individuals who resided in Ouro Preto.

Assessment of exposure to manganese in welding operations during the assembly of heavy excavation machinery accessories.

Welder exposure to metals in various industrial sectors is poorly characterized. We had the opportunity to carry out an exploratory study to characterize manganese exposure in welding operations in a recently established Quebec factory that assembled accessories for heavy excavation machinery. Ten workers were sampled for total manganese for at least two consecutive days out of three followed by two consecutive days for respirable manganese (with a size selective sampler with a median cut-off of 4 microns), during a typical week in the summer of 1998. Parts being welded were characterized as large or small. Small parts were those being welded on tables during subassembly. Workers were divided into two groups according to the parts they were welding. Seventy-eight percent of the total manganese exposure levels of welding operations during the assembly of large accessories of heavy excavation machinery exceeded the manganese American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit value (TLV) of 0.20 mg/m3 (GM 0.24 mg/m3, n = 14) while none exceeded the TLV during the assembly of small pieces (GM 0.06 mg/m3, n = 8). Welding operations during the assembly of large heavy excavation machinery accessories may pose a significant health hazard. Considering the importance of task-related variables affecting exposure among workers, further studies are needed to better characterize exposure determinants of welding operations during the assembly of heavy excavation machinery accessories.

Potential of dandelion (Taraxacum officinale) as a bioindicator of manganese arising from the use of methylcyclopentadienyl manganese tricarbonyl in unleaded gasoline.

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic manganese (Mn) compound currently added to unleaded gasoline in Canada. It has been suggested that the combustion of MMT containing Mn could cause various deleterious health effects in animals and humans at very high concentrations. This study evaluates the potential of dandelions (Taraxacum officinale) as bioindicators of Mn environmental contamination. Samples were picked at three different distances from a highway: a highly exposed site (E++), a lightly exposed site (E+) and a control site (E), located respectively at 10, 50 and 100 m. The total Mn, Mg, Ca, Al, Fe and Zn concentrations were measured in the soils and in the plants (flower, stem, leaves and root) by neutron activation analysis. Exchangeable Mn was measured in soils by atomic absorption spectrophotometry. Mn concentrations of the different parts of the plant and exchangeable Mn in soils were not correlated with distance from the roadway and, thus, do not seem to be a sensitive indicator of Mn contamination. Soil Mn concentrations were correlated with distance from the roadway. This suggests the hypothesis that the environmental fate of Mn from MMT sources could be associated with an increased total Mn in soil but does not lead to an increase in exchangeable Mn.

Manganese deposition in basal ganglia structures results from both portal-systemic shunting and liver dysfunction.

BACKGROUND & AIMS: Manganese (Mn) deposition could be responsible for the T(1)-weighted magnetic resonance signal hyperintensities observed in cirrhotic patients. These experiments were designed to assess the regional specificity of the Mn increases as well as their relationship to portal-systemic shunting or hepatobiliary dysfunction. METHODS: Mn concentrations were measured in (1) brain samples from basal ganglia structures (pallidum, putamen, caudate nucleus) and cerebral cortical structures (frontal, occipital cortex) obtained at autopsy from 12 cirrhotic patients who died in hepatic coma and from 12 matched controls; and from (2) brain samples (caudate/putamen, globus pallidus, frontal cortex) from groups (n = 8) of rats either with end-to-side portacaval anastomosis, with biliary cirrhosis, or with fulminant hepatic failure as well as from sham-operated and normal rats. RESULTS: Mn content was significantly increased in frontal cortex (by 38%), occipital cortex (by 55%), pallidum (by 186%), putamen (by 66%), and caudate (by 54%) of cirrhotic patients compared with controls. Brain Mn content did not correlate with patient age, etiology of cirrhosis, or history of chronic hepatic encephalopathy. In cirrhotic and portacaval-shunted rats, Mn content was increased in pallidum (by 27% and 57%, respectively) and in caudate/putamen (by 57% and 67%, respectively) compared with control groups. Mn concentration in pallidum was significantly higher in portacaval-shunted rats than in cirrhotic rats. No significant changes in brain Mn concentrations were observed in rats with acute liver failure. CONCLUSIONS: These findings suggest that brain Mn deposition results both from portal-systemic shunting and from liver dysfunction.

Airborne manganese particulates and methylcyclopentadienyl manganese tricarbonyl (MMT) at selected outdoor sites in Montreal.

This study aims to assess the atmospheric concentrations of methylcyclopentadienyl manganese tricarbonyl (MMT), respirable manganese (MNR) and total manganese (MnT) in certain specific microenvironments and to provide an estimation of human exposure to MnR. Sampling was carried out in five microenvironments: a gas station, an underground car park, downtown Montreal, near an expressway and near an oil refinery. The samples were collected using Gil-Air portable pumps during three days and were analyzed by instrumental neutron activation analysis (INAA). The mean concentrations of MnR, MnT and MMT were 0.036 microgram m-3, 0.103 microgram m-3 and 0.005 microgram m-3 respectively. The MnR/MnT ratios vary from 25% to 43% (mean 35%) while the MMT/MnT ratios averaged about 5%. Furthermore, the mean concentration of the MnR measured near the expressway (0.053 microgram m-3) is similar to the United States Environmental Protection Agency (U.S. EPA) reference concentration (RfC = 0.05 microgram m-3). The average daily environmental exposure dose to MNR is estimated at 0.010 microgram kg-1 d-1 and its contribution to the multimedia exposure (air, food and water) is low. The overall results show a lack of potential exposure to MMT and substantial concentrations of MnR near an expressway.

Environmental contamination and human exposure to manganese--contribution of methylcyclopentadienyl manganese tricarbonyl in unleaded gasoline.

The organomanganese compound MMT (methylcyclopentadienyl manganese tricarbonyl), an antiknock additive in unleaded gasoline, has been used in Canada since 1976. Indeed, Canada is the only country where MMT is almost exclusively used. In October 1995, by court decision the Environmental protection Agency (EPA) granted Ethyl's waiver for the use of MMT in the United States. Paradoxically, in 1997 the federal government of Canada adopted a law (C-29) that banned both the interprovincial trade and the importation for commercial purposes of manganese-based substances, including MMT. However, MMT is currently widely used in Canada because of substantial stockpiling, and six Canadian provinces are challenging the law in the courts. Moreover, MMT has been approved for use in Argentina, Australia, Bulgaria, Russia, and conditionally, in New Zealand. It has been suggested by some scientists that combustion of MMT may be a significant source of exposure to inorganic Mn in urban areas. The crucial question is whether Mn contamination from industrial sources combined with the additional contamination that would result from the widespread use of MMT would lead to toxic effects. Our research efforts have attempted to assess the environmental/ecosystem Mn contamination arising from the combustion of MMT in abiotic and biotic systems as well as human exposure. The experimental evidence acquired so far provides useful information on certain environmental consequences of the use of MMT as well as raising a number of questions. Our results gave evidence indicating that roadside air, soils, plants, and animals may be contaminated by Mn. As well, some specific groups of the population could have a higher level of exposure to Mn. Nevertheless, the levels of exposure remain below international guide values. Further studies and further characterization of dose-response relationships are thus needed to provide successful implementation of evidence-based risk-assessment approaches.

Bioaccumulation of manganese and its toxicity in feral pigeons (Columba livia) exposed to manganese oxide dust (Mn3O4).

Manganese tetroxide (Mn3O4) is a product from the combustion of methylcyclopentadienyl manganese tricarbonyl. Exposure to high levels of manganese can lead to serious health effects especially to the central nervous and respiratory systems. Very few studies on the effects of long-term low level exposure to Mn3O4 have been reported. The present study was therefore conducted to examine the bioaccumulation and toxicity of manganese in various organs of feral pigeons (Columba livia) when exposed to low levels of Mn3O4 via inhalation and hence to find any possible relationship between these two parameters. A total of 22 pigeons was exposed to 239 micrograms/m3 of manganese for 7 h/day, 5 days/week for 5, 9, and 13 consecutive weeks. Manganese concentrations in various tissues, e.g., brain (mesencephalon), lung, liver, intestine, pancreas, kidney, muscle, bone, and whole blood, were measured by neutron activation analysis. Various biochemical parameters in blood, e.g., hematocrit, total proteins, glucose, uric acid, alanine aminotransferase, total iron, blood urea nitrogen and triglycerides, were also measured. Manganese concentrations in brain, lung, and bone were significantly higher in Mn3O4-exposed pigeons (0.59, 0.58, and 3.02 micrograms wet tissue, respectively) than in the control group (0.46, 0.19, 1.74 micrograms/g wet tissue, respectively). However, except for total proteins such exposure did not produce any changes in various biochemical parameters which were within the normal values. Thus these results have shown that, despite significant bioaccumulation of manganese in some tissues, no significant toxic effects could be seen.

Role of manganese in the pathogenesis of portal-systemic encephalopathy.

Amongst the potential neurotoxins implicated in the pathogenesis of hepatic encephalopathy, manganese emerges as a new candidate. In patients with chronic liver diseases, manganese accumulates in blood and brain leading to pallidal signal hyperintensity on T1-weighted Magnetic Resonance (MR) Imaging. Direct measurements in globus pallidus obtained at autopsy from cirrhotic patients who died in hepatic coma reveal 2 to 7-fold increases of manganese concentration. The intensity of pallidal MR images correlates with blood manganese and with the presence of extrapyramidal symptoms occurring in a majority of cirrhotic patients. Liver transplantation results in normalization of pallidal MR signals and disappearance of extrapyramidal symptoms whereas transjugular intrahepatic portosystemic shunting induces an increase in pallidal hyperintensity with a concomitant deterioration of neurological dysfunction. These findings suggest that the toxic effects of manganese contribute to extrapyramidal symptoms in patients with chronic liver disease. The mechanisms of manganese neurotoxicity are still speculative, but there is evidence to suggest that manganese deposition in the pallidum may lead to dopaminergic dysfunction. Future studies should be aimed at evaluating the effects of manganese chelation and/or of treatment of the dopaminergic deficit on neurological symptomatology in these patients.

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 contamination and human exposure assessment to manganese in the St-Lawrence River ecozone (Quebec, Canada) using an environmental fate/exposure model: GEOTOX.

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used as an additive in unleaded gasoline. The combustion of MMT leads to the formation of oxides of manganese. The objective of the present study is to predict the environmental levels of Mn and the human exposure in the St-Lawrence ecozone (fluvial section, Quebec, Canada) using an environmental fate/exposure model: GEOTOX. The results of our MMT research program on abiotic and biotic components of the ecosystem and on the human exposure were used to validate the model estimations. Air and surface soil were selected as source terms with an annual Mn input rate in each compartment of 0.083-0.113 mol km-2 d-1 and 0.44-0.87 mol km-2 d-1 respectively (Mn3O4 equivalent). The predicted air, soil, plant, surface water and sediment concentrations were similar (+/- 50%) to values measured in the Montreal region. As expected, the ingestion pathway was the main absorption route for adults (> 99%), with vegetables and fruits contributing almost 80% of the dietary intake of Mn. The multimedia exposure doses for adult men predicted by the model ranged between 0.04 and 0.08 mg kg-1 d-1 compared to 0.004 and 0.201 mg kg-1 d-1 (average = 0.05) for workers from the MMT study. Considering the landscape configuration and the source vectors (air and soil) included in the model, GEOTOX estimations were in good agreement with measured values.

Increased blood manganese in cirrhotic patients: relationship to pallidal magnetic resonance signal hyperintensity and neurological symptoms.

Increasing evidence suggests that manganese deposition is responsible for the T1-weighted magnetic resonance imaging (MRI) signal hyperintensity consistently observed in pallidum of cirrhotic patients. However, the relationship between blood manganese and the etiology or severity of liver disease, as well as the neurological symptomatology in these patients, has not been well established. In the present study, blood manganese concentrations were measured by atomic absorption spectrometry together with MRI and neurological evaluation in 57 cirrhotic patients with various etiologies and severity of liver disease. Blood manganese concentrations were elevated in 67% of cirrhotic patients and were significantly higher in patients with previous portacaval anastomoses or transjugular intrahepatic portosystemic shunt (TIPS). Pallidal signal hyperintensity was observed in 88% of patients, and significant correlations were demonstrated between blood manganese and pallidal index (PI) (a measure of pallidal signal hyperintensity), as well as Child-Pugh score. Assessment of extrapyramidal symptoms using the Columbia rating scale revealed a significant incidence of tremor, rigidity, or akinesia in up to 89% of cirrhotic patients. However, there was no significant correlation between blood manganese and extrapyramidal symptoms, although severity of akinesia was significantly greater in Child-Pugh C patients. Extrapyramidal symptoms could result from a toxic effect of manganese on basal ganglia dopaminergic function. These findings further support a role for manganese in the etiology of pallidal MRI signal hyperintensity in patients with chronic liver disease.

Exposure of taxi drivers and office workers to total and respirable manganese in an urban environment.

This research measured the exposure of two groups of workers to respirable and total manganese (Mn) and characterized the Mn particles emitted from an automobile tailpipe. The exposure of 20 office workers and 9 taxi drivers in Toronto to total airborne Mn and respirable Mn was measured over a 7-day period, 24 hours per day. Subjects were asked to wear two pumps (one included a size-selective cyclone that collected the respirable particles), and two battery chargers were supplied to each person so that the pump batteries could be recharged overnight while sampling continued. All filters were analyzed by neutron activation. In addition, Mn particles emitted from a car were collected directly at the exhaust. Particles were observed using secondary electron images in a scanning electron microscope (SEM), and their elemental composition was determined by energy dispersive x-ray spectrometry. The Mn concentrations obtained for the group of office workers ranged from 0.001 to 0.034 microgram/m3 for respirable Mn and from 0.002 to 0.044 microgram/m3 for total Mn. For the taxi drivers the Mn concentrations ranged from 0.007 to 0.032 microgram/m3 for respirable Mn and from 0.008 to 0.073 microgram/m3 for total Mn. There was a significant difference (p < 0.05) between the two groups for both respirable and total Mn. SEM analysis showed that the particles were mostly heterogeneous agglomerates varying from 1 to 100 microns. Even if the specific exposure to Mn from automobiles has not been directly established, these results suggest that the related increase of exposure may be limited.

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.

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 microgram/m3) than the blue-collar workers (0.04 microgram/m3). However, the contribution of atmospheric Mn to the total absorbed dose was less than 1%, and well below the standards established 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 microgram/100 ml) and fall within the normal adult range. The average hair Mn concentrations were significantly higher for the garage mechanics (0.66 microgram/g) than for the blue-collar workers (0.39 microgram/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 in drinking water and its contribution to human exposure]. / Le manganèse dans l'eau potable et sa contribution à l'exposition humaine.

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an additive in unleaded gasoline. The combustion of MMT leads to the emission of Mn oxides to the environment and may represent a potential risk to public health. It therefore seems important to assess the associated Mn exposure. The present study is part of a broader research program on total human exposure to Mn and aims specifically at assessing the level of exposure to Mn and other metals via drinking water. A comparative study was performed between two groups of workers (garage mechanics and blue collar workers of the University of Montreal) differentiated by their exposure to inhaled Mn. For Pb, Cu and Zn in residential tap water, significant differences were observed between the first sample and the one taken after one minute of flow. A significant difference was also found between the two groups of workers (combined flow time) for Mn, Cu and Ca. The Mn contribution from water is estimated to be 1% of the total dose from ingested food. This low exposure may become important (17%) for persons drinking well water, especially if we consider interactions between metals following multimedia exposure.