Use of CALPUFF to predict airborne Mn levels at schools in an urban area impacted by a nearby manganese alloy plant

Children are susceptible to the health effects derived from elevated manganese (Mn) environmental exposure; residents living in urban areas where ferromanganese alloy plants are located are usually exposed to high Mn levels. In this work, a dispersion model developed by the USEPA, CALPUFF, has been used to estimate the airborne Mn levels near educational centers located in Santander bay, Northern Spain, an urban area where high Mn levels have been measured in the last decade. The CALPUFF model was validated in a previous work from a multi-site one-year observation dataset. Air manganese levels in 96 primary, secondary and high schools located in Santander bay were estimated using the CALPUFF model for two months corresponding to warm and cold periods using real meteorological data and Mn emission rates corresponding to different emission scenarios. Results show that when the emission scenario that best represented the observations dataset is used, the air Mn levels exceed the WHO guideline (i.e. 150?ng?Mn/m3) in 24% and 11% of the studied schools in the cold and warm periods respectively. These exceedances depend on the distance from the FeMn alloy plant and the direction of the prevailing winds. Additional emission scenarios based on the implementation of preventive and corrective measures are simulated and analysed in terms of the number of exceedances of the WHO guideline. The age range of children has been also considered in the analysis.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the CTM2013-43904R Project. This funding source was not involved in the study design; data collection, analysis, or interpretation; the writing of the article; or the decision to submit for publication

Monitoring the levels of particle matter-bound manganese: an intensive campaign in an urban/industrial area

The aim of this work is to monitor the manganese levels in the particulate matter throughout the Santander Bay, an urban/industrial area located in the region of Cantabria (northern Spain). Previous studies developed in the region have shown high concentrations of manganese in ambient air according to the World Health Organization (WHO) criteria, most likely due to the presence of a ferromanganese alloy plant in the area. An intensive PM10 sampling campaign has been carried out for a year in nine monitoring sites (one per month) by means of a low volume sequential sampling device (2.3 m3 /h) equipped with a 15 filter cartridge. 28 samples have been collected in each location onto 47 mm quartz fiber filters. The filters were subjected to microwave assisted acid digestion (HNO3:H2O2 with a mixture of 8:2 ml) based on UNE-EN 14902:2006. Inductively coupled plasma mass spectrometry (ICP-MS) was then used for metal analysis. In addition to Mn, also Ti, V, Fe, Ni, Cu, Zn, As, Mo, Cd, Sb and Pb were analyzed. According to the results obtained in the present sampling campaign, the highest daily manganese level at Santander Bay reached 3200 ng/m3 with a monthly average higher than the 150 ng/m3 established by the WHO as an annual average guideline value in six monitoring sites (up to 713.9 ng/m3 ). The highest manganese levels were found at N-NE of the ferroalloy plant, which agrees with the prevailing winds (S/SW). Although monthly samplings have been carried out in each location, these results suggest that manganese concentrations in ambient air in some sites of the Santander Bay would exceed the WHO recommendation. In addition, the strong linear relationship found between Mn and V, Fe, As, Cd and Pb in the vicinities of the plant suggests that the presence of some of these metals in the area may be also related to this activity.This work has been financially supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the Project CTM2013-43904R. Ana Hernández Pellón also thanks the Ministry of Economy and Competitiveness (MINECO) for the FPI grant awarded BES-2014-068790

A comparative study between the fluxes of trace elements in bulk atmospheric deposition at industrial, urban, traffic, and rural sites

The input of trace elements via atmospheric deposition towards industrial, urban, traffic, and rural areas is quite different and depends on the intensity of the anthropogenic activity. A comparative study between the element deposition fluxes in four sampling sites (industrial, urban, traffic, and rural) of the Cantabria region (northern Spain) has been performed. Sampling was carried out monthly using a bulk (funnel bottle) sampler. The trace elements, As, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Ti, Zn, and V, were determined in the water soluble and insoluble fractions of bulk deposition samples. The element deposition fluxes at the rural, urban, and traffic sites followed a similar order (Zn>Mn>>Cu=Ti>Pb>V=Cr>Ni>>As=Mo>Cd). The most enriched elements were Cd, Zn, and Cu, while V, Ni, and Cr were less enriched. An extremely high deposition of Mn was found at the industrial site, leading to high enrichment factor values, resulting from the presence of a ferro-manganese/silicomanganese production plant in the vicinity of the sampling site. Important differences were found in the element solubilities in the studied sites; the element solubilities were higher at the traffic and rural sites, and lower at the urban and industrial sites. For all sites, Zn and Cd were the most soluble elements, whereas Cr and Ti were less soluble. The inter-site correlation coefficients for each element were calculated to assess the differences between the sites. The rural and traffic sites showed some similarities in the sources of trace elements; however, the sources of these elements at the industrial and rural sites were quite different. Additionally, the element fluxes measured in the insoluble fraction of the bulk atmospheric deposition exhibited a good correlation with the daily traffic volume at the traffic site.The authors are grateful for the financial support from the CTM 2010-16068 (Spanish Ministry of Science and Innovation) and CTM 2013-43904 R (Spanish Ministry of Economy and Competitiveness) projects. The “Consejería de Medio Ambiente” from the Cantabria Government is also acknowledged for sending the report on the background levels of heavy metals and trace elements in soils in the Cantabria region. The authors are also grateful to “Ayuntamiento de Camargo” for helping us with the sampling site of Maliaño

Quantification of manganese species in particulate matter collected in an urban area nearby a manganese alloy plant

A sequential extraction test was used to evaluate the manganese (Mn) species in PM10 samples collected in an urban area impacted by a Mn alloy plant, where the annual guideline value for Mn in air according to the World Health Organization (WHO) is frequently exceeded (i.e. > 150 ng m−3). The average Mn level in this campaign was 208.6 ng m−3, reaching maximum daily values up to 1138.9 ng m−3. Manganese species were dominated by water-soluble Mn (49.9%), followed by metallic Mn (Mn0) and Mn2+ (27.1%), insoluble Mn (14.6%), and Mn3+ and Mn4+(8.8%). This study reveals, on one hand, the higher fraction of water-soluble Mn species present in atmospheric aerosols in comparison with aerosols collected in work environments of the Mn alloy industry, which is attributed to the reaction between emitted Mn oxides and gaseous pollutants (SO2, NO2 and HCl) during transport in the atmosphere. On the other hand, there was a non-negligible fraction of more toxic species (Mn3+ and Mn4+), which are more potent than Mn2+ to induce reactive oxygen species.This work was financially supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the CTM2013-43904R Project. Ana Hernández-Pellón would like to thank the Ministry of Economy and Competitiveness for the FPI grant awarded, reference number BES-2014-068790

Variability in metal deposition among industrial, rural and urban areas in the Cantabria region (Northern Spain)

Cantabria is a small region located in Northern Spain that combines different land uses; thus, urban, industrial and rural areas are present in a relatively small area (5300 km2); however, the anthropogenic influence is evident by studying the deposition of metals towards these areas. Three sampling sites (industrial, urban and rural) were selected to assess the variability in metal deposition. Sampling was carried out monthly (from January 2012 to July 2012) using a bulk (funnelbottle) sampler. As, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Ti, Zn and V were determined in the water-soluble and in the insoluble fractions of deposition samples. The impact of the human activities in the industrial area can be seen on several metals such as Pb, Zn, Cu and Mn. The most obvious influence was found for Mn, high fluxes were measured in the industrial site with a mean value of 2260 μg/m2·day; in contrast to urban (99.6 μg/m2·day) and rural (15.3 μg/m2·day) areas. The lowest flux values were found in the rural area for all the elements. Enrichment Factor (EF) analysis were also studied for the three sites. The high EFs values found for Pb, Mn, Cu, and Zn (>100) in the industrial site point to significant anthropogenic sources, mainly originated from industrial activities (steel and ferro-manganese alloy manufacturing plants) and road traffic

Metal(loid) bioaccessibility and inhalation risk assessment: A comparison between an urban and an industrial area

The content of metal(loid)s in particulate matter (PM) is of special concern due to their contribution to overall (PM) toxicity. In this study, the bioaccessibility and human health risk of potentially toxic metal(loid)s associated with PM10 were investigated in two areas of the Cantabrian region (northern Spain) with different levels of exposure: an industrial area mainly influenced by a ferromanganese alloy plant; and an urban area consisting mainly of residential and commercial activities, but also affected, albeit to a lesser extent by the ferroalloy plant. Total content and bioaccessible fractions in simulated lung fluids (SLFs) of Fe, Mn, Zn, Ni, Cu, Sb, Mo, Cd and Pb were determined by ICP-MS. Gamble's solution and artificial lysosomal fluid (ALF) were used to mimic different conditions inside the human respiratory system. A health risk assessment was performed based on the United States Environmental Protection Agency's (USEPA) methodology. Most metal(loid)s showed moderate and high bioaccessibility in Gamble's solution and ALF, respectively. Despite the high variability between the samples, metal(loid) bioaccessibility was found to be higher on average at the industrial site, suggesting a greater hazard to human health in the proximity of the main metal(loid) sources. Based on the results of the risk assessment, the non-carcinogenic risk associated with Mn exposure was above the safe limit (HQ> 1) under all the studied scenarios at the industrial site and under some specific scenarios at the urban location. The estimated carcinogenic inhalation risk for Cd exposure at the industrial site was found to be within the range between 1.0 × 10−6 to 1.0 × 10−4 (uncertainty range) under some scenarios. The results obtained in this study indicate that Mn and Cd inhalation exposure occurring in the vicinities of the studied areas may pose a human health risk.This work was financially supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the CTM2013–43904R Project. Ana Hernández-Pellón would like to thank the Ministry of Economy and Competitiveness (MINECO) for the FPI and research stay grants awarded, reference numbers BES-2014-068790 and EEBB-I-17-12031

Personal inhalation exposure to manganese and other trace metals in an environmentally exposed population: bioaccessibility in size-segregated particulate matter samples

Exposure to environmental airborne manganese (Mn) can lead to neurotoxic disorders and cognitive deficits. The degree of exposure can be assessed by personal sampling of particulate matter (PM) or through biomarkers of exposure. The aim of this work was to characterise the personal exposure to airborne Mn and other trace metals by measuring their bioaccessibility in PM filters taken from personal samplers in an environmentally exposed adult population living in the vicinity of a ferromanganese alloy plant in Santander Bay (northern Spain). Concentrations of bioaccessible and non-bioaccessible Mn and other metals associated with coarse (PM10-2.5) and fine (PM2.5) modes were quantified from 24 h personal samplers in 130 participants divided into two groups according to their Mn exposure: highly (n = 65) and moderately (n = 65) exposed. Gastric fluid and artificial lysosomal fluid (ALF) were used in the bioaccessibility tests as surrogate agents for the body fluids that can come into contact with coarse and fine particles, respectively. The mean air Mn levels in PM10-2.5 and PM2.5 were 127.2 and 126.2 ng/m3, respectively, in the highly exposed group, and 18.6 and 31.7 ng/m3 in the moderately exposed group. The bioaccessibility (%) of Mn in gastric fluid and ALF was also found to be greater in the highly exposed group. The results indicate that people living near Mn alloy plants have an increased potential health risk for Mn exposure due to higher total air Mn concentrations and bioaccessibility.This work was funded by the Spanish Ministry of Science, Innovation and Universities through Project CTM 2017-82636-R. Bohdana Markiv also thanks the same Ministry for her PhD grant, PRE 2018-085152

Estimation of PM10-bound manganese concentration near a ferromanganese alloy plant by atmospheric dispersion modelling

Numerous studies have associated air manganese (Mn) exposure with negative health effects, primarily neurotoxic disorders. This work presents a description of the emission and dispersion of PM10-bound Mn from industrial sources in the Santander bay area, Northern Spain. A detailed day-specific emission estimation was made and assessed for the main Mn source, a manganese alloy production plant under 8 different scenarios. Dispersion analysis of PM10-bound Mn was performed using the CALPUFF model. The model was validated from an observation dataset including 101 daily samples from four sites located in the vicinities of the manganese alloy plant. Model results were in reasonable agreement with observations (r= 0.37; NMSE= 2.08; Fractional Bias= 0.44 and Modelled/Observed ratio = 1.57). Simulated and observed Mn concentrations in the study area were much higher than the guidelines proposed by the World Health Organization (WHO) and the U.S. Environmental Protection Agency (USEPA), highlighting the need to reduce the Mn concentrations in the area. Based on the analysis of the Mn source contribution from the ferromanganese alloy plant, some preventive and corrective measures are discussed at the end of the paper. This work shows that CALPUFF dispersion model can be used to predict PM10-bound Mn concentrations with reasonable accuracy in the vicinities of industrial facilities allowing the exposure assessment of the nearby population, which can be used in future epidemiological studies.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the Project CTM2013-43904R. The authors also acknowledge the Spanish State Meteorology Agency (AEMET) for providing meteorological and atmospheric sounding data for the period of study

Estimating airborne heavy metal concentrations in Dunkerque (northern France)

This work aims to estimate the levels of lead (Pb), nickel (Ni), manganese (Mn), vanadium (V) and chromium (Cr) corresponding to a 3-month PM10 sampling campaign conducted in 2008 in the city of Dunkerque (northern France) by means of statistical models based on partial least squares regression (PLSR), artificial neural networks (ANNs) and principal component analysis (PCA) coupled with ANN. According to the European Air Quality Directives, because the levels of these pollutants are sufficiently below the European Union (EU) limit/target values and other air quality guidelines, they may be used for air quality assessment purposes as an alternative to experimental measurements. An external validation of the models has been conducted, and the results indicate that PLSR and ANNs, with comparable performance, provide adequate mean concentration estimations for Pb, Ni, Mn and V, fulfilling the EU uncertainty requirements for objective estimation techniques, although ANNs seem to present better generalization ability. However, in accordance with the European regulation, both techniques can be considered acceptable air quality assessment tools for heavy metals in the studied area. Furthermore, the application of factor analysis prior to ANNs did not yield any improvements in the performance of the ANNs.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the Projects CTM2010-16068/CTM2013-43904R and the FPI short stay EEBB-I-13-07691. Germán Santos would also like to thank the Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV) at La Maison de la Recherche en Environnement Industriel for welcoming him as a guest PhD student in their facilities