Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Manganese content of Tradescancia species exposed to automotive combustion of methylcyclopentadienyl manganese tricarbonyl in urban and rural landscapes

The purpose of this study is to assess the effect of manganese (Mn) from methylcyclopentadienyl manganese tricarbonyl (MMT) on grass (Tradescancia) species beside the major urban and rural highways in the greater Toronto area. Grass clippings were collected at distances up to 40 m from the roadside of a wooded, weakly exposed site (E+) and two unwooded, highly exposed sites (E++ and E+++) to Mn contamination. Statistical tests, including analysis of variance and correlation coefficients, were used to compare the Mn deposition on grass species with respect to distance and traffic density. A higher deposition of Mn was expected at the highly exposed sites when compared with the weakly exposed site, but a significantly higher concentration of Mn was observed at weakly exposed rural E+ site (Mn = 54.07 microg/g; dry wt) than the highly exposed urban E++ (Mn = 38.17 microg/g; dry wt) and E+++ (Mn = 35.63 microg/g; dry wt) sites. A significant correlation coefficient was found for Mn and traffic density (r2 = 0.311, p = 0.0074) at the weakly exposed site than at the highly exposed (r2 = 0.1589, p = 0.1052) urban sites. These data demonstrate that despite the continuous use of MMT in Canadian gasoline, the levels do not appear to exceed the worldwide tolerable levels (17-334 g/g; dry wt) in grass species inhabiting ecosystems next to major highways in urban regions.     

Fluoride Emissions and Forest Growth

Abstract

The October 1995 court decision allowing Ethyl Corporation to offer methylcyclopentadienyl manganese tricarbonyl (MMT) for sale to refiners for introduction into unleaded gasoline as an octane enhancer is likely to result in increased fine (PM_2.5) manganese (Mn) concentrations in ambient air. Concern exists regarding possible health effects. In this paper, recent fine Mn concentrations in three monitoring networks and one U.S. Environmental Protection Agency (EPA) study of personal exposure are analyzed. One network consists mainly of rural sites in national parks in the United States, a second consists mainly of urban sites in California, and the third consists mainly of urban sites in Canada where MMT has been used for a number of years. During the late 1980s and early 1990s, mean ambient concentrations ranged from 1 ng/m³ in the mostly rural network to 3 ng/m³ in the mostly urban California network to 12 ng/m³ in the MMT-impacted Canadian network. Several lines of evidence suggested that some of the fine Mn observed in the United States during the 1986-1992 period was contributed by automobiles using leaded gasoline, for which MMT was a registered fuel additive. However, the near-disappearance of leaded gasoline has resulted in a very small portion of fine Mn being attributed to automobiles in the years since 1992.A source apportionment analysis suggested that crustal contributions to ambient fine Mn are on the order of 1-2 ng/m³ in both the United States and Canada.     

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.     

Trend and concentrations of legacy lead (Pb) in highway runoff

This study presents the results of lead (Pb) concentrations from both highway runoff and contaminated soil along 32 and 23 highway sites, respectively. In general, the Pb concentration on topsoil (0-15 cm) along highways was much higher than the Pb concentration in subsurface soil (15-60 cm). The Pb deposited on soil appears to be anthropogenic and a strong correlation was found between the Pb concentration in surface soil and highway runoff in urban areas. The concentration of Pb measured during 1980s from highways runoff throughout the world was up to 11 times higher than the measured values in mid 1990 s and 2000s. The current Pb deposited on soil near highways appears to be a mixture of paint, tire weight balance and old leaded gasoline combustion. Overall, the Pb phase-out regulation reduced the Pb deposits in the environment and consequently lowered Pb loading into receiving waters.     

Comment on “Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Fate of Manganese Exhaust Products”

In an article published in the August 1975, Journal of the Air Pollution Control Association entitled “Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Pate of Manganese Exhaust Products,” the authors conclude that, “… use of MMT in gasoline will result in no public health hazards, because of the low toxicity of manganese and because of the very low concentration of MMT that would be used in gasoline …. If all gasoline contained 0.1 g Mn/gal, the amount of airborne Mn its exhaust would contribute to urban areas would contribute to urban areas would be only 0.02-0.2 μg/m³, with a median value of 0.05 μg/m³.”     

Methylcyclopentadienyl Manganese Tricarbonyl as an Antiknock: Composition and Fate of Manganese Exhaust Products

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been marketed as a combustion improver for fuel oil and turbine fuel. Use concentrations for this purpose are about 0.025 g manganese/gal in fuel oil and 0.08 to 0.5 g/gal in turbine fuels. In addition, it has been used to a small extent in gasoline.     

Estimating distributions of long-term particulate matter and manganese exposures for residents of Toronto,Canada

Methylcyclopentadienyl manganese tricarbonyl (MMT), a manganese-based gasoline additive, has been used in Canadian gasoline for about 20 yr. Because MMT potentially increases manganese levels in particulate matter resulting from automotive exhausts, a population-based study conducted in Toronto, Canada assessed the levels of personal manganese exposures. Integrated 3-day particulate matter (PM_2.5) exposure measurements, obtained for 922 participant periods over the course of a year (September 1995–August 1996), were analyzed for several constituent elements, including Mn. The 922 measurements included 542 participants who provided a single 3-day observation plus 190 participants who provided two observations (in two different months). In addition to characterizing the distributions of 3-day average exposures, which can be estimated directly from the data, including the second observation for some participants enabled us to use a model-based approach to estimate the long-term (i.e. annual) exposure distributions for PM_2.5 mass and Mn. The model assumes that individuals’ 3-day average exposure measurements within a given month are lognormally distributed and that the correlation between 3-day log-scale measurements k months apart (after seasonal adjustment) depends only on the lag time, k, and not on the time of year. The approach produces a set of simulated annual exposures from which an annual distribution can be inferred using estimated correlations and monthly means and variances (log scale) as model inputs. The model appeared to perform reasonably well for the overall population distribution of PM_2.5 exposures (mean=28 μg m^-3). For example, the model predicted the 95th percentile of the annual distribution to be 62.9 μg m^-3 while the corresponding percentile estimated for the 3-day data was 86.6 μg m^-3. The assumptions of the model did not appear to hold for the overall population of Mn exposures (mean=13.1 ng m^-3). Since the population included persons who were potentially occupationally exposed to Mn (in non-vehicle-related jobs), we used responses to questionnaire items to form a subgroup consisting of non-occupationally exposed participants (671 participant periods), for which the model assumptions did appear to hold. For that subpopulation (mean=9.2 ng m^-3), the model-predicted 95th percentile of the annual Mn distribution was 16.3-ng m^-3, compared with 21.1 ng m^-3 estimated for the 3-day data.     

Advances in the Analysis of Air Contaminants Comments

Abstract

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 (Mn_R) and total (Mn_T) 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. Mn_R and Mn_T and other metals were measured on Teflon filters by neutron activation. Mn exposure doses by inhalation were calculated using Monte–Carlo simulations. Mn_R and Mn_T average concentrations were significantly higher at site C⁺ (Mn_R = 0.024 µg m^-3; Mn_T = 0.050 µg m^-3) than at site C^- (Mn_R= 0.015 µg m^-3; Mn_T= 0.027 µg m^-3). Temporal profiles at sites C⁺ and site C^-were similar, with a coefficient of correlation of 0.24 for Mn_R and 0.26 for Mn_T. Trend analyses (ARIMA) also showed that the period of the week (work days vs. off days) was significantly related to Mn_R and Mn_T variations at both sites. The average exposure dose by inhalation to Mn_R and Mn_T ranged from 0.001 to 0.030 µg kg^-1 day^-1 and 0.001 to 0.05 µg kg^-1 day^-1. Mn_R and Mn_T 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 Mn_R and Mn_T 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.     

Survey on composition and bioconcentration potential of 12 metallic elements in King Bolete (Boletus edulis) mushroom that emerged at 11 spatially distant sites

This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.     

A Numerical Model of Diffusion of Carbon Monoxide near Highways

A numerical model, which can be used to study the dispersion of carbon monoxide emissions from automobiles traveling on a highway, is described. The model Is based upon the semi-empirical equation of turbulent diffusion. The performance of the model has been tested using carbon monoxide concentration data obtained near highway 401 in the city of Toronto, Canada.     

Particulate matter and manganese exposures in Toronto,Canada

Methylcyclopentadienyl manganese tricarbonyl (MMT) is a manganese-based gasoline additive used to enhance automobile performance. MMT has been used in Canadian gasoline for about 20 yr. Because of the potential for increased levels of Mn in particulate matter resulting from automotive exhausts, a large-scale population-based exposure study (∼1000 participant periods) was conducted in Toronto, Canada, to estimate the distribution of 3-day average personal exposures to particulate matter (PM_2.5 and PM₁₀) and Mn. A stratified, three-stage, two-phase probability, longitudinal sample design of the metropolitan population was employed. Residential indoor and outdoor, and ambient levels (at a fixed site and on a roof) of PM_2.5, PM₁₀, and Mn were also measured. Supplementary data on traffic counts, meteorology, MMT levels in gasoline, personal occupations, and activities (e.g. amount of vehicular usage) were collected. Overall precision (%RSD) for analysis of duplicate co-located samples ranged from 2.5 to 5.0% for particulate matter and 3.1 to 5.5% for Mn. The detection limits were 1.47 and 3.45 μg m^-3 for the PM₁₀ and PM_2.5 fractions, respectively, and 5.50 and 1.83 ng m^-3 for Mn in PM₁₀ and PM_2.5, respectively. These low detection limits permitted the reporting of concentrations for >98% of the samples. For PM₁₀, the personal particulate matter levels (median 48.5 μg m^-3) were much higher than either indoor (23.1 μg m^-3) or outdoor levels (23.6 μg m^-3). The median levels for PM_2.5 for personal, indoor, and outdoor were 28.4, 15.4 and 13.2 μg m^-3, respectively. The correlation between PM_2.5 personal exposures and indoor concentrations was high (0.79), while correlations between personal and the outdoor, fixed site and roof site were low (0.16–0.27). Indoor Mn concentration distributions (in PM_2.5 and PM₁₀), unlike particulate matter, exhibited much lower and less variable levels that the corresponding outdoor data. The median personal exposure was 8.0 ng m^-3, compared with 4.7 and 8.6 ng m^-3, respectively, for the indoor and outdoor distributions. The highest correlations occurred for personal vs indoor data (0.56) and for outdoor vs roof site data (0.66), and vs fixed site data (0.56). The concentration of Mn in particulate matter, expressed in ppm (w/w), revealed that the fixed site was the highest, followed by the roof site, outdoor, indoor, and personal. The personal and indoor data showed a statistically significant correlation (0.68) while all other correlations between personal or indoor data and outdoor or fixed-site data were quite small. The low correlations of personal and indoor levels with outdoor levels suggest that different sources in the indoor and outdoor microenvironments produce particle matter with dissimilar composition. The correlation results indicate that neither the roof- nor fixed-site concentrations can adequately predict personal particulate matter or Mn exposures.     

Arsenic release from arsenic-bearing Fe-Mn binary oxide: effects of E(h) condition

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E_h ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E_h range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E_h range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E_h ranges were also proposed.     

Manganese levels and chemical fractionation in street dust in South Africa

Mn in street dust and soil from selected roads was studied to assess the contribution of combustion of vehicular methylcyclopentadienyl manganese tricarbonyl (MMT) to Mn levels and distribution in Pretoria, South Africa. Total Mn concentrations ranged from (329.1-863.9 μg g⁻¹) for dust and (215.8-450.6 μg g⁻¹) for soil. These values were significantly higher than the mean value (278.9 μg g⁻¹) found on soil from a rural environment in Pretoria. The lowest value for the dust sample (329.1 μg g⁻¹) was close to the mean background level of 330 μg g⁻¹ for Mn in soil. Mn distribution in the samples was most in the residual fraction (178.18-487.50 μg g⁻¹) and (140.76-293.40 μg g⁻¹) for dust and soil respectively. Mn in the other fractions were 56.45-202.60 μg g⁻¹ oxides, 90.71-45.34 μg g⁻¹ organic, 45.36-12.65 μg g⁻¹ carbonates and 1.98-6.72 μg g⁻¹ exchangeable for dust and 32.54–167.31 μg g⁻¹ oxides, 34.23–70.45 μg g⁻¹ organic, 10.98-30.45 μg g⁻¹ carbonate and 1.0-4.87 μg g⁻¹ exchangeable for soil. Major source of Mn determined was mainly from the combustion of vehicular MMT.     

Study of metal concentrations in the environment near diesel transport routes

In recent years, a river-dredging project has been executed in Nantou, Taiwan. A large number of diesel vehicles carrying gravel and sand shuttle back and forth on the main traffic roads (Tai-16 and Tai-21). The purpose of this study is to figure out the levels of metals contributed by those vehicles to the surrounding environment. Eight stations along the roadside of diesel transport routes were selected as exposure sites, while a small village located about 9 km away from the diesel transport routes was selected as the control site. The mass concentrations of coarse and fine particulate matter indicated that contributions from traffic fleets resulted in a higher percentage of coarse particulate matter in the ambient air at exposure sites in comparison with that at control site. Significantly higher values of EC (elemental carbon) concentrations and ratios of EC/OC (organic carbon) at exposure sites indicate that diesel vehicles at exposure sites contributed a greater amount of pollutants than gasoline vehicles. Exposure site concentrations for all metals measured (Fe, Al, Mn, Pb, Zn, Cu, Ni, Mo and As) for fine and coarse particulate matter were all higher than those at the control site. Recorded levels of metal contents in road dust and riverside soil near Tai-16 and Tai-21 showed that while the traffic fleet did not increase the metal contents of crustal elements in the road dust, it did significantly increase the metal contents of traffic-related elements. Enrichment factors (EFs) were calculated with respect to road dust (EF_road) and with respect to the samples of riverside soil (EF_river). Among these metals, Mo was the most highly-enriched metal. The extremely high EF_river value (4300) of Mo indicates that these stations were highly polluted by diesel emission. Whereas the significantly high EF_road value (810) of Mo implies that a considerable of Mo was emitted from tailpipe of diesel vehicles.     

Elemental uptake by seaweed, Plocamium corallorhirza along the Kwazulu-natal coast of Indian Ocean, South Africa

This study reports the elemental uptake by Plocamium corallorhiza, a Rhodophyta class of coralline alga grown richly along KwaZulu-Natal coastline. The uptake of seven important elements, namely Fe, Mn, As, B, Ti, Zn and Hg, selected based on their abundance in the samples, were investigated for a one-year cycle, from June 2002 to May 2003, at four chosen sites located along the KwaZulu-Natal coastline. The sites spread over 150 km from North to South Coast are Zinkwasi, Ballito, Treasure Beach and Park Rynie. P. corallorhiza possess good manganese and arsenic-accumulating ability and has potential to be an excellent indicator for most of the metals studied. A typical P. corallorhiza sample at Park Rynie (winter) recorded Mn (14 ppm), Fe (6.02 ppm), As (8.4 ppm), B (1580 ppb), Zn (234 ppb), Ti (751 ppb) and Hg (15.8 ppb). The general trend found at all sites was a large decrease in iron concentration in spring and summer and increase in winter. Mercury uptake was lowest in winter and autumn at all sites. The highest mercury levels in the seaweeds were recorded during spring or summer.     

Levels of polycyclic aromatic hydrocarbons in Canadian mountain air and soil are controlled by proximity to roads

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in soil and XAD-based passive air samples taken from a total of 22 sites along three transects (Revelstoke, Yoho, and Observation, 6-8 sites for each transect) in the mountains of Western Canada in 2003-2004. Median concentrations in air (4-ring PAHs: 33 pg/m³) were very low and comparable to those in global background regions such as the Arctic. Low median soil concentrations (16 EPA PAHs: 16 ng/g dry weight) and compositional profiles dominated by naphthalene and phenanthrene are similar to those of tropical soils, indicative of remote regions influenced mostly by PAHs from traffic and small settlements. Comparing levels and composition of PAHs in soils between and along transects indeed suggests a clear relationship with proximity to local sources. Sampling sites that are closer to major traffic arteries and local settlements have higher soil concentrations and a higher relative abundance of heavier PAHs than truly remote sites at higher elevations. This remains the case when the variability in soil organic carbon content between sites is taken into account. Both air/soil concentration ratios and fugacity fractions suggest atmospheric net deposition of four-ring PAHs to soils.     

Elemental Uptake by Seaweed,Plocamium corallorhirza Along the KwaZulu-Natal Coast of Indian Ocean,South Africa

This study reports the elemental uptake by Plocamium corallorhiza, a Rhodophyta class of coralline alga grown richly along KwaZulu-Natal coastline. The uptake of seven important elements, namely Fe, Mn, As, B, Ti, Zn and Hg, selected based on their abundance in the samples, were investigated for a one-year cycle, from June 2002 to May 2003, at four chosen sites located along the KwaZulu-Natal coastline. The sites spread over 150 km from North to South Coast are Zinkwasi, Ballito, Treasure Beach and Park Rynie. P. corallorhiza possess good manganese and arsenic-accumulating ability and has potential to be an excellent indicator for most of the metals studied. A typical P. corallorhiza sample at Park Rynie (winter) recorded Mn (14 ppm), Fe (6.02 ppm), As (8.4 ppm), B (1580 ppb), Zn (234 ppb), Ti (751 ppb) and Hg (15.8 ppb). The general trend found at all sites was a large decrease in iron concentration in spring and summer and increase in winter. Mercury uptake was lowest in winter and autumn at all sites. The highest mercury levels in the seaweeds were recorded during spring or summer.     

Seasonal variation of monomethylmercury concentrations in surface sediments of the Tagus Estuary (Portugal)

Surface sediments (0-2cm) were collected at 40 sites along the Tagus Estuary in July and December 2004. The sediments were analysed for total mercury, monomethylmercury (MMHg) and interpretative parameters (e.g. redox potential, pH, C(org)). No significant differences in total Hg, pH, Al, Fe, Mn and C(org) were found between sediments collected in the two periods, but MMHg concentrations were higher in July. On average sediments were warmer and more reducing in summer. On the basis of these results, an increase of 7kg of MMHg (+37%) in surface sediments of the Tagus Estuary was estimated. Presumably higher temperatures in summer promote the increase of microbial activity and higher methylation rates. The alterations observed in this study point to the potential importance of seasonal changes in MMHg production at surface sediments with eventual changes in the MMHg uptake by benthic invertebrates and other organisms in the food web.     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.