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Gastric bioaccessibility is a conservative measure of nickel bioavailability after oral exposure: Evidence from Ni-contaminated soil, pure Ni substances and Ni alloys
2021
Dutton, Michael D. | Thorn, Ryan | Lau, Wilson | Vasiluk, Luba | Hale, Beverly
Oral bioaccessibility (BAc) is a surrogate for the bioavailability (BAv) of a broad range of substances, reflecting the value that the approach offers for assessing oral exposure and risk. BAc is generally considered to have been validated as a proxy for oral BAv for the important soil contaminants Pb, Cd, and As. Here, using literature data for Ni BAc and BAv, we confirmed that Ni BAc (gastric only, with HCl mimicking stomach conditions) is a conservative measure of BAv for the oral exposure pathway. Measured oral BAv of Ni in soil was shown to be 50–100 times less than the simplest oral BAc estimates (%BAv = 0.012(%BAc) - 0.023 (r = 0.701, 95%CI [0.456, 0.847], n = 30)) in rats, demonstrating a significant conservatism for exposure assessment. The relationship between the oral BAv and BAc of nickel sulfate hexahydrate (NSHH) was comparable to that of soil, with measured oral BAv of NSHH (1.94%) being a small fraction of NSHH gastric BAc (91.1%). BAc and BAv reflect the underlying Ni speciation of the sample, with the bioaccessible leaching limits being represented by the highly soluble Ni salts and the poorly soluble Ni monoxide, and the environmental (e.g. soil properties) or gastric (e.g. food present) conditions. BAc has potential utility for chemical classification purposes because pure Ni substances can be grouped by %BAc values(using standardized methodologies for the relevant exposure routes), these groupings reflecting the underlying chemistry and speciation of the samples of substances tested here, with 0.008% %BAc for alloys (SS304, SS316, Inconel, Monel), <1% in green NiO and Ni metal massives, 0.9–23.6% for Ni powders, 9.8–22.7% for Ni sulfides, 26.3–29.6% for black oxidic Ni, and 82–91% for the soluble Ni salts. Oral BAc provides realistic yet conservative estimates of BAv for the hazard classification and risk assessment of Ni substances.
Show more [+] Less [-]Characterization and source apportionment of single particles from metalworking activities
2021
Arndt, Jovanna | Healy, Robert M. | Setyan, Ari | Flament, Pascal | Deboudt, Karine | Riffault, Véronique | Alleman, Laurent Y. | Mbengue, Saliou | Wenger, John C.
Industrial metalworking facilities emit a variety of air toxics including volatile organic compounds, polycyclic aromatic hydrocarbons (PAHs) and heavy metals. In order to investigate these emissions, a 1-month multi-instrument field campaign was undertaken at an industrial site in Grande-Synthe, Dunkirk (France), in May and June 2012. One of the main objectives of the study was to provide new information on the chemical composition of particulate matter with aerodynamic diameters smaller than 2.5 μm (PM₂.₅) in the vicinity of metalworking facilities. An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed to provide size-resolved chemical mixing state measurements of ambient single particles at high temporal resolution. This mixing state information was then used to apportion PM₂.₅ to local metalworking facilities influencing the receptor site. Periods when the site was influenced by metalworking sources were characterised by a pronounced increase in particles containing toxic metals (manganese, iron, lead) and polycyclic aromatic hydrocarbons (PAHs) with a variety of chemical mixing states. The association of specific particle classes with a nearby ferromanganese alloy manufacturing plant was confirmed through comparison with previous analysis of raw materials (ores) and chimney filter particle samples collected at the facility. Particles associated with emissions from a nearby steelworks were also identified. The contribution of local metalworking activities to PM₂.₅ at the receptor site for the period when the ATOFMS was deployed ranged from 1 to 65% with an average contribution of 17%, while the remaining mass was attributed to other local and regional sources. These findings demonstrate the impact of metalworking facilities on air quality downwind and provide useful single particle signatures for future source apportionment studies in communities impacted by metalworking emissions.
Show more [+] Less [-]Distributions, sources and pollution status of 17 trace metal/metalloids in the street dust of a heavily industrialized city of central China
2013
Li, Zhonggen | Feng, Xinbin | Li, Guanghui | Bi, Xiangyang | Zhu, Jianming | Qin, Haibo | Dai, Zhihui | Liu, Jinling | Li, Qiuhua | Sun, Guangyi
A series of representative street dust samples were collected from a heavily industrialized city, Zhuzhou, in central China, with the aim to investigate the spatial distribution and pollution status of 17 trace metal/metalloid elements. Concentrations of twelve elements (Pb, Zn, Cu, Cd, Hg, As, Sb, In, Bi, Tl, Ag and Ga) were distinctly amplified by atmospheric deposition resulting from a large scale Pb/Zn smelter located in the northwest fringe of the city, and followed a declining trend towards the city center. Three metals (W, Mo and Co) were enriched in samples very close to a hard alloy manufacturing plant, while Ni and Cr appeared to derive predominantly from natural sources. Other industries and traffic had neglectable effects on the accumulation of observed elements. Cd, In, Zn, Ag and Pb were the five metal/metalloids with highest pollution levels and the northwestern part of city is especially affected by heavy metal pollution.
Show more [+] Less [-]Long-term study of palladium in road tunnel dust and sewage sludge ash
2008
Leopold, K. | Maier, M. | Weber, S. | Schuster, M.
The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg−1 were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg−1 were found in the years 1986–1997. In both matrices correlations of Pd content to Pd demand of industry are discussed. This work reveals the link between intensified industrial Pd use and Pd content in according environmental samples.
Show more [+] Less [-]Fabrication of activated carbon supported modified with bimetallic-platin ruthenium nano sorbent for removal of azo dye from aqueous media using enhanced ultrasonic wave
2022
Herein, activated carbon supported modified with bimetallic-platin ruthenium nano sorbent (PtRu@AC) was synthesized by a thermal decomposition process and used in the removal of methylene blue (MB) from aqueous solutions. The synthesized nano sorbents were characterized by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS) spectroscopic techniques. The data obtained from characterization studies showed that PtRu@AC nano sorbent was highly crystalline and in a form of PtRu alloy with a monodispersed composition. The results indicated that the maximum adsorption capacity (qemax) for the removal of MB with PtRu@AC under optimum conditions was detected to be 1.788 mmol/g (569.4 mg/g). The experimental kinetic results of the study revealed that the adsorption of methylene blue was found to be more compatible with the false second-order model compared to some tested models. Calculations for thermodynamic functions including enthalpy change (ΔHo), entropy change (ΔSo), and Gibbs free energy change (ΔGo) values were performed to get an idea about the adsorption mechanism. As a result, the synthesized PtRu@AC nano adsorbent was detected as a highly effective adsorbent material in the removal of MB from aquatic mediums.
Show more [+] Less [-]Manganese and lead levels in settled dust in elementary schools are correlated with biomarkers of exposure in school-aged children
2018
Rodrigues, Juliana L.G. | Bandeira, Matheus J. | Araújo, Cecília F.S. | dos Santos, Nathália R. | Anjos, Ana Laura S. | Koin, Ng Lai | Pereira, Laiz C. | Oliveira, Sérgio S.P. | Mergler, Donna | Menezes-Filho, José A.
Previously, we showed that manganese (Mn) levels in settled dust in elementary schools increased at a rate of 34.1% per km closer to a ferro-manganese alloy plant in the rainy season. In this study, we investigated how this environmental pollution indicator varied in the dry season and if there was an association with Mn biomarker levels in school-aged children. Dust samples were collected with passive samplers (disposable Petri dishes) placed in interior and exterior environments of 14 elementary schools. Occipital hair, toenails and blood samples were collected from 173 students aged 7–12 years from three of these schools, with varying distance from the industrial plant. Mn and lead (Pb) levels were measured by graphite furnace atomic absorption spectrometry. Mn concentration geometric means (GM) in dust fall accumulation in interior environments of schools located at 2, 4, 6 and > 6 km-radii from the plant were 2212, 584, 625 and 224 μg Mn/m2/30 days, respectively. The modelled rate of change of dust Mn levels decreases by 59.8% for each km further from the plant. Pb levels in settled dust varied between 18 and 81 μg/m2/30 days with no association with distance from the plant. Blood lead levels median (range) were 1.2 μg/dL (0.2–15.6), of which 97.8% were <5 μg/dL. Mn in hair and toenails were 0.66 μg/g (0.16–8.79) and 0.86 μg/g (0.15–13.30), respectively. Mn loading rates were positively associated with log MnH (β = 1.42 × 10−5, p < 0.001) after adjusting for children's age; and also with log MnTn (β = 2.31 × 10−5, p < 0.001) independent of age. Mn loading rates explained 18.5% and 28.5% of the variance in MnH and MnTn levels, respectively. School-aged children exposure to Mn, independently of age, increases significantly with school proximity to the ferro-manganese alloy plant.
Show more [+] Less [-]Spatial-temporal variability of metal pollution across an industrial district, evidencing the environmental inequality in São Paulo
2020
Locosselli, Giuliano Maselli | Moreira, Tiana Carla Lopes | Chacón-Madrid, Katherine | Arruda, Marco Aurélio Zezzi | Camargo, Evelyn Pereira de | Kamigauti, Leonardo Yoshiaki | da Trindade, Ricardo Ivan Ferreira | Andrade, Maria de Fátima | André, Carmen Diva Saldiva de | André, Paulo Afonso de | Singer, Julio M. | Saiki, Mitiko | Zaccarelli-Marino, Maria Angela | Saldiva, Paulo H. N. (Paulo Hilário Nascimento) | Buckeridge, Marcos Silveira
Although air pollution decreased in some cities that shifted from an industrial to a service-based economy, and vehicular emission regulation became more restrictive, it is still a major risk factor for mortality worldwide. In central São Paulo, Brazil, air quality monitoring stations and tree-ring analyses revealed a decreasing trend in the concentrations of particulate matter and metals. Such trends, however, may not be observed in industrial districts located in the urban periphery, where the usual mobile sources may be combined with local stationary sources. To evaluate environmental pollution in an industrial district in southeastern São Paulo, we assessed its spatial variability, by measuring magnetic properties and concentrations of Al, Ba, Ca, Cl, Cu, Fe, K, Mg, Mn, P, S, Sr, Zn in the bark of 62 trees, and its temporal trends, by measuring Cd, Cu, Ni, Pb, V, Zn in tree rings of three trees. Source apportionment analysis based on tree barks revealed two clusters with high concentrations of metals, one related to vehicular and industrial emissions (Al, Ba, Cu, Fe, Zn) in the east side of the industrial cluster, and the other related to soil resuspension (Cu, Zn, Mn) in its west side. These patterns are also supported by the magnetic properties of bark associated with iron oxides and titanium-iron alloy concentrations. Dendrochemical analyses revealed that only the concentrations of Pb consistently decreased over the last four decades. The concentrations of Cd, Cu, Ni, V, and Zn did not significantly decrease over time, in contrast with their negative trends previously reported in central São Paulo. This combined biomonitoring approach revealed spatial clusters of metal concentration in the vicinity of this industrial cluster and showed that the local population has not benefited from the decreasing polluting metal concentrations in the last decades.
Show more [+] Less [-]Scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and aerosol time-of-flight mass spectrometry (ATOFMS) single particle analysis of metallurgy plant emissions
2016
Arndt, J. | Deboudt, K. | Anderson, A. | Blondel, A. | Eliet, S. | Flament, P. | Fourmentin, M. | Healy, R.M. | Savary, V. | Setyan, A. | Wenger, J.C.
The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe–Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.
Show more [+] Less [-]Addressing aquatic hazard classification for metals, metal compounds and alloys in marine systems
2016
Huntsman-Mapila, P. | Skeaff, J.M. | Pawlak, M. | Beaudoin, R.
New International Maritime Organization regulations require shippers to classify all solid bulk cargo to indicate whether they are Harmful to the Marine Environment (HME). The objective of this work was to adapt the freshwater Transformation/Dissolution Protocol (T/DP) to marine water to provide a method to determine, when compared with marine Ecotoxicity Reference Values (ERVs), whether a metal-bearing substance is HME. The substances examined were: Cu2O powder; Ni metal powder; Co3O4 powder; and a Ni–Co–Fe alloy, as wire cuttings, which were the same substances examined in the freshwater T/D validation study and afforded comparisons of the reactivity, or measure of the rate and extent of metal release from the metal-bearing substances in freshwater versus marine conditions. The marine T/D method is suitable for conducting examinations of metal-bearing substances with a wide range of reactivities, from the relatively reactive Cu2O powder and the alloy to the Co3O4 powder, which was the least reactive.
Show more [+] Less [-]Combining geochemical and chemometric tools to assess the environmental impact of potentially toxic elements in surface sediment samples from an urban river
2020
da Silva Júnior, Jucelino Balbino | Abreu, Ilene Matanó | de Oliveira, Daiane Aparecida Francisco | Hadlich, Gisele Mara | de Albergaria Barbosa, Ana Cecília Rizzatti
This article investigates sediments collected from the banks of the Subaé River located in Todos os Santos Bay in the state of Bahia, Brazil, in 2018, twenty-five years after the closing of a former lead alloy processing plant. Ten sediment samples were collected at different points of the course of the river and its estuarine region. Chemometric tools were used to determine geochemical correlations between the organic matter content and concentration of sulfides and potentially toxic metals. The inorganic geochemical variables (enrichment factor [EF]) used in this evaluation were concentrations of the Pb, Cd, Cu, Zn, and Ni. Chemical element analyses were performed using ICP-OES. To assess the interaction between metals and sulfide or metals and organic matter, concentrations of Pb, Cd, Cu, Zn, Ni, sulfide, and the silt-clay fraction constituted the organic geochemical parameters selected to characterize the amount of organic matter present in Subaé River sediment samples, determining the carbon content (%TOC) to compose the matrix of the principal component analysis (PCA) and hierarchical cluster analysis. PCA showed that 88.3% of the samples were representative for assessing correlations between geochemical variables. A tendency toward binding was found among Cu, Cd, Ni, and sulfide, as well as the silt-clay fraction. The concentrations (mg kg⁻¹) of lead, zinc, and copper were higher in both collection campaigns, ranging from 4.72 to 31.34, 12.76 to 54.24, and 5.34 to 31.37, respectively. Pb and Zn were presented in elemental form when assessed as a function of the pH and Eh of the environment. Except for Cd (EF: 0.51 to 5.49), the other elements exhibited little or no potential pollution in the aquatic environment of the Subaé River.
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