Using multi-site data to apportion PM-bound metal(loid)s: Impact of a manganese alloy plant in an urban area

The identification and quantification of the PM emission sources influencing a specific area is vital to better assess the potential health effects related to the PM exposure of the local population. In this work, a multi-site PM10 sampling campaign was performed in seven sites located in the southern part of the Santander Bay (northern Spain), an urban area characterized by the proximity of some metal(loid) industrial sources (mainly a manganese alloy plant). The total content of V, Mn, Fe, Ni, Cu, Zn, As, Mo, Cd, Sb and Pb was determined by ICP-MS. This multi-site dataset was evaluated by positive matrix factorization(PMF) in order to identify the main anthropogenic metal(loid) sources impacting the studied area, and to quantify their contribution to the measured metal(loid) levels. The attribution of the sources was done by comparing the factor profiles obtained by the PMF analysis with representative profiles from known metal(loid) sources in the area, included in both the European database SPECIEUROPE (V2.0) and the US database EPA-SPECIATE (V4.5) or calculated from literature data. In addition, conditional bivariate probability functions (CBPF)s were used to assist in the identification of the sources. Four metal(loid) sources were identified: Fugitive and point source emissions from the manganese alloy plant (49.9% and 9.9%, respectively), non-exhaust traffic emissions (38.3%) and a minor source of mixed origin (1.8%). The PMF analysis was able to make a clear separation between two different sources from the manganese alloy plant, which represented almost 60% of the total measured metal(loid) levels, >80% of these emissions being assigned to fugitive emissions. These results will be useful for the assessment of the health risk associated with PM10-bound metal(loid) exposure and for the design of efficient abatement strategies in areas impacted by similar industries.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 grant awarded, reference number BES-2014-068790

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

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

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

Levels and sources of polycyclic aromatic hydrocarbons in the soluble fraction of the atmospheric deposition in Cantabria (northern Spain)

The aim of this work is to assess the levels of polycyclic aromatic hydrocarbons (PAHs) in the soluble fraction of the bulk atmospheric deposition in four sites of a small region located in northern Spain (Cantabria). Samples were collected monthly for two years at an urban site (Santander), and for one year at an industrial (Maliaño), rural (Bárcena Mayor) and traffic (Cabezón de la Sal) sites. Samples were filtered and the filtrate was extracted, concentrated, purified and analysed for 15 PAHs: acenaphthylene (ACY), acenaphthene (ACE), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLA), pyrene (PYR), benzo[a]anthracene (BaA), chrysene (CHR), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (IcdP), dibenzo[a,h]anthracene (DahA), and benzo[ghi]perylene (BghiP). The highest deposition fluxes of PAHs were found at the industrial site (Maliaño); the total PAH fluxes at the other sites were similar. Box plots of the PAH levels found in the literature in wet and bulk deposition samples were used to compare the values observed in this work. FLA, BaA, PHE and PYR were the most abundant PAHs at the industrial site. At the urban and rural site, the profile found in the deposition samples was similar: PHE>FLA>BaA>PYR. The traffic site showed a different profile: PYR>ANT>FLU>FLA. A preliminary source identification study was made by calculating diagnostic ratios of some PAH isomers (FLA/(FLA+PYR) and BaA/(BaA+CHR)); these ratios were compared with those found for the main PAH industrial and non-industrial sources in the region.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the Projects CTM2010-16068 and CTM2013-43904R

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

New challenges and applications of supported liquid membrane systems based on facilitated transport in liquid phase separations of metallic species

The linear economic model based on "take-make-dispose" has become unsustainable, revealing the necessity of shifting towards a circular economy (CE) approach, in which secondary raw materials play a key role in closing material cycles. In this context, industrial effluents with metallic content, are considered a potential secondary source for these elements, the lack of the availability of the appropriate technology being the main barrier when implementing circular economy principles at industrial scale. In this regard, supported liquid membrane (SLM) systems based on facilitated transport may be decisive. Thus, the objective of this research paper is to show the potential of facilitated transport systems to foster the transition to a more sustainable management of industrial metallic effluents. To accomplish that, three different applications of supported liquid membrane systems in acidic industrial effluents will be presented: a) Zn/Fe separation, b) Ni/Cd separations and c) Removal of hexavalent Cr. Additionally, the recovery and separation of two different critical raw materials, i.e. Li and rare earth elements will be discussed. Although facilitated transport systems have been successfully applied to both, Zn/Fe and Ni/Cd separation, as well as to hexavalent Cr removal, further work should be done for the successful recovery and separation of Li and rare earths with supported liquid membrane systems, especially in terms of selectivity improvement and validation with real industrial effluents.Financial support from the Spanish Ministry of Science, Innovation and Universities under the projects PID2020-115409RB-I00 and RTI2018-093310-B-I00 are gratefully acknowledged

Urban air concentration and deposition of manganese and physico-chemical characterization of manganesebearing particles.

RESUMEN: La contaminación atmosférica es un problema de dimensiones globales. La presencia de metales y metaloides en aire ambiente es especialmente relevante en áreas urbanas e industriales. En este contexto, el objetivo de esta tesis doctoral es la determinación del origen, los niveles en aire (totales y bioaccesibles) y las tasas de deposición de los principales metales y metaloides contenidos en el PM10 muestreado en la Bahía de Santander (Cantabria), un área urbano-industrial influida por varias actividades antropogénicas, principalmente por una planta de fabricación de aleaciones de Mn situada en la zona sur de la mencionada bahía. Además, el presente trabajo también incluye la evaluación de las características físico-químicas de las partículas relacionadas con la actividad de dicha planta, así como la realización de un análisis del riesgo sobre la salud, basado en la metodología de la U.S. EPA, para la población expuesta a las emisiones de esta actividad.ABSTRACT: Atmospheric pollution is a problem of global dimensions. The presence of metals and metalloids in air is especially relevant in urban and industrial areas. In this context, the objective of this doctoral thesis is to determine the origin, levels in air (total and bioaccessible) and atmospheric deposition rates of the main metal and metalloids present in the PM10 collected in the Santander Bay (Cantabrian Region), an urban-industrial area influenced by several anthropogenic activities, mainly a Mn alloy plant located in the southern part of this Bay. In addition, the present work also includes the evaluation of the physico-chemical characteristics of the particles related to the mentioned plant, as well as the development of a health risk assessment, based on the U.S. EPA methodology, for the population exposed to the emissions from this activity.El presente trabajo ha sido financiado por el Ministerio de Economía y Competitividad de España (MINECO) a través del proyecto “Manganeso en aire urbano: Niveles en concentración y depósito, caracterización físicoquímica y modelización mediante modelos de dispersión” CTM2013-43904R. Durante la ejecución del presente trabajo, su autora, Ana María Hernández Pellón, ha disfrutado de una ayuda predoctoral para la formación de doctores del Ministerio de Economía y Competitividad de España (MINECO) concedido por resolución de 16 de marzo de 2015, con referencia BES- 2014-068790. Asimismo, la autora ha disfrutado de una ayuda a la movilidad predoctoral del Ministerio de Economía y Competitividad de España (MINECO), con referencia EEBB-I-17-12031, para la realización de una estancia breve de tres meses de duración en el “Institute of Chemical Technologies and Analytics” perteneciente a la “Vienna University of Technology” (TU Wien) en Austria. Por ello, Ana María Hernández Pellón expresa su más sincero agradecimiento a dichas institucione

Corrosion and sustainability : a problem pending to solve

Ingeniería químic