Impact of COVID-19 restrictions on hourly levels of PM10, PM2.5 and black carbon at an industrial suburban site in northern Spain.

Due to the COVID-19 pandemic, lockdown restrictions were established around the world. Many studies have assessed whether these restrictions affected atmospheric pollution. Comparison between them is difficult as the periods of time considered are generally not the same and thus, different conclusions may be reached. Besides, most of them consider mean daily pollutant concentration, despite differences being observed according to the time of day. In this study, the hourly levels of PM10, PM2.5 and black carbon (BC) in an industrial suburban area in the north of Spain were analysed from May 2019 to June 2020 and compared with those from the literature, using the same period in each case. In general, the highest concentrations were reached when the wind direction came from the southwest (where a steelworks, a coal-fired power plant and other industries are located) and during the night-time, both before and during the lockdown. The highest concentrations of PM10, PM2.5 and BC were observed from December to February (on average: 45, 17 and 1.3 µg m-3, respectively). The decrease/increase in those pollutants levels during the lockdown were found to be highly dependent on the period considered. Indeed, PM10 can be found to decrease by up to 39% or increase by 12%; PM2.5 can decrease by 21% or increase by up to 36%; and BC, although it generally decreases (by up to 42%), can increase by 7.4%.

Impact of COVID-19 restrictions on the dry deposition fraction of settleable particulate matter at three industrial urban/suburban locations in northern Spain.

Ninety 24-h samples of the dry deposition fraction of settleable particulate matter (DSPM) were collected at one suburban industrial site ('EMA') and two urban industrial sites ('Lauredal' and 'Laboratory') in the western area of Gijón (North of Spain) from December 2019 to June 2020. The levels registered point to an environmental issue that should receive close attention from environmental authorities. Before lockdown restrictions due to COVID-19 were established, all samples collected at the EMA site exceeded 300 mg·m-2·d-1 (the Spanish limit value until 2002). Large amounts of DSPM were also registered at the Lauredal and Laboratory sites, maximum levels reaching 1039.2 and 672.7 mg·m-2·d-1, respectively. Seven metals were analysed in DSPM samples: Al, Ca, Fe, K, Mg, Mn and Na. Fe reached the highest values: 2473.4, 463.4 and 293.3 mg·m-2·d-1 (EMA, Lauredal and Laboratory sites, respectively). This study quantifies the reductions in the DSPM levels registered (on average, 97.2, 73.5 and 90.5% at the EMA, Lauredal and Laboratory sites, respectively) during the lockdown, which involved the restriction of population mobility and industrial activity. The influence of wind speed and its direction were also assessed to better understand the role of these restrictions in the observed reductions. The concentrations of all the metals in the DSPM were reduced by more than 75%, on average, except for K at the Laboratory and Lauredal sites. These decreases were much higher than those found by other authors for smaller fractions of the atmospheric particulate matter (PM10, PM2.5). The findings of the present study highlight the importance of DSPM in highly industrialized urban/suburban locations and indicate the direction that legal measures might take, given the influence of anthropogenic emissions.

Relationship Between Exposure to Sulphur Dioxide Air Pollution, White Cell Inflammatory Biomarkers and Enzymatic Infarct Size in Patients With ST-segment Elevation Acute Coronary Syndromes.

Aims: To analyse the relationship among air pollutants, markers of inflammation and infarct size in patients with acute coronary syndrome (ACS). Methods: This was a prospective analysis of consecutive patients admitted to hospital because of ACS. Cardiac biomarkers were drawn. The daily mean values of the air pollutants from the day before until 7 days before admission were analysed. The study population was stratified according to infarct size, based on median peak troponin value. Results: Patients were divided into two groups of 108 subjects each, according to median peak troponin value. Patients with extensive MIs had a higher neutrophil:lymphocyte ratio and leukocyte and neutrophil counts than patients with smaller MIs. In addition, they were exposed to higher concentrations of sulphur dioxide (9.7 ± 4.1 versus 8.4 ± 3.1 µg/m3; p=0.009) and lower concentrations of ozone (33.8 ± 13.7 versus 38.6 ± 14.5 µg/m3; p=0.014). Multivariate analysis showed that sulphur dioxide levels (OR 1.12; 95% CI [1.031-1.21]; p=0.007) and neutrophil/lymphocyte ratio (OR 1.08; 95% CI [1.011-1.17]; p=0.024) were independent predictors of infarct size. Conclusion: Patients with extensive MIs had higher white cell inflammatory levels and had been exposed to higher sulphur dioxide concentrations in the ambient air.

Settleable matter in a highly industrialized area: Chemistry and health risk assessment.

Settleable particulate matter (SPM) was collected at two sampling points within an urban area highly affected by nearby industrial activities. Total deposition values up to 386 mg ·m-2·d-1 were registered, the majority of samples exceeding the limit value established in the legislation in force in Spain until 2002 (300 mg·m-2·d-1). Dry deposition values showed high variability (8.6-830.3 mg·m-2·d-1). Forty-one metals and metalloids were analysed in the dry fraction of SPM, the main being Fe and Ca (maximums: 304.4 and 68.6 mg·m-2·d-1, respectively), followed by Al, Mg, Na, K, Mn, Ti, P and Zn. Trace elements like As and Pb reached up to 7.3 and 76.3 µg·â€¯m-2·d-1, respectively. Strong correlations (r > 0.90, p-value < 0.05) between Fe and other elements (Ca, Mn and Pb) were found at both sampling sites. Scanning electron microscopy confirmed the presence of these particles rich in Fe and Ca, in addition to other components, whose morphologies pointed out to anthropogenic sources. These results combined with meteorology data suggest a common industrial source contributing to the levels of these metals. Furthermore, a human health risk study was carried out to assess the potential carcinogenic and non-carcinogenic risks of exposure to thirteen elements in these particles (Al, As, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sb, Sr, V and Zn). The highest levels of risk seemed to be associated with the presence of As, Pb and Sb.

Anthropogenic and meteorological influences on PM10 metal/semi-metal concentrations: Implications for human health.

There is growing interest in investigating the human health risk associated with metals in airborne particulate matter. The objective of this paper is the health risk assessment of Al, Be, Sb, Sn, Ti and Tl in PM10 under different advections of air masses. These metals/semi-metal were studied in samples collected in an area influenced by industrial activities in northern Spain with the aim of analysing the variations in PM10 metal/semi-metal. Elemental concentrations were assessed over a period of one year in terms of air mass origin by means of back trajectories (HYSPLIT), the conditional probability function, polar plots, PM concentration roses, aerosol maps (NAAPs) and receptor modelling. The mean concentrations of Al, Be, Sb, Sn, Ti and Tl were 254, 0.02, 1.30, 1.15, 15.3 and 0.20  ng/m3, respectively, and were within the usual range for suburban stations in Europe. The highest levels were recorded during conditions of regional air mass origin, highlighting the importance of sources not far from the station. Under these circumstances, the renovation of air masses was not produced. The main sources of metals were anthropogenic, mostly related to the use of coal and coke production. In general, the cancer and non-cancer risk values obtained in this study fell within accepted precautionary criteria in all trajectory groups. However, in order to improve air quality and reduce risks to human health, the impact resulting from the joint inhalation of Al, Be, Sb, Sn, Ti and Tl should not be ignored when air masses are fundamentally of regional origin.

Suburban air quality: Human health hazard assessment of potentially toxic elements in PM10.

PM10 samples were collected at two suburban locations in northern Spain, a traffic-industrial suburban (TIS) station located in the coastal city of Gijón and an industrial suburban (IS) station in Langreo, about 25 km inland. The aerosol samples were chemically analysed to determine ambient air concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V and Zn. The results showed that the mean levels of As, Co, Cu, Fe, Mn, Ni, Pb and Se recorded at the IS location were higher than those at the TIS station. Mean levels of Fe and Zn in PM10 were higher than all other species at both the TIS and IS sampling sites (467 and 353 ng Fe/m3 and 46 and 282 ng Zn/m3, respectively). Human exposure to these twelve potentially toxic elements through PM10 was assessed for both children and adults using the U.S.EPA method, considering three pathways: ingestion, dermal contact and inhalation. In general, the IS location presented higher non-cancer risks than the TIS site. However, at both suburban locations, cancer and non-cancer risk values were in the acceptable range for adults, some exceptions being found. Greater health risk was estimated in the case of children. For this sector of the population, ingestion, dermal contact and/or inhalation of As, Pb and Zn in PM10 may pose a health hazard owing to possible carcinogenic/non-carcinogenic effects.

Enrichment factors to assess the anthropogenic influence on PM10 in Gijón (Spain).

Thirty-two chemical species were determined in PM10 sampled at a suburban site on the north coast of Spain. Enrichment factors were applied to infer their soil/non-soil origin. The geochemical ratios were calculated using two databases: soil composition from locations in the surroundings of the sampling station and the Earth's average upper-crust composition. In the present study, dissimilarities were found between the enrichment factors obtained using these two databases. Al, Ti, La and Ce were taken as the reference elements to normalise the data, reaching analogous conclusions. Bi, Cd, Cu, Sb, Se, Sn and Zn were associated with predominantly non-soil apportionments. As the relevance of soil/non-soil sources for the other analysed elements was found to be variable, they were probably of mixed origin. Furthermore, pairs of elements showed strong relationships, thus pointing to a common origin. Na-Mg and Co-Ni, with Pearson correlation coefficients above 0.9, were respectively related to marine and industrial apportionments. Enrichment factors have proved to be a useful tool to distinguish the soil/non-soil origin of chemical species present in airborne particulate matter. However, the choice of the reference database for soil composition considerably determined the accuracy of the conclusions.

Relationship between physico-chemical characteristics and potential toxicity of PM10.

PM10 was sampled at a suburban location affected by traffic and industry in the north of Spain. The samples were analysed to determine the chemical components of PM10 (organic and elemental carbon, soluble chemical species and metals). The aim of this study was to assess the toxicity of PM10 in terms of the bulk analysis and the physico-chemical properties of the particles. Total carbon, sulphates, ammonium, chlorides and nitrates were found to be the major constituents of PM10. The contribution of the last of these was found to increase significantly with PM10 concentration (Pearson coefficient correlation of 0.7, p-value < 0.001). Individual airborne particles were characterised morphologically and chemically via a combination of Scanning Electron Microscopy and Energy-Dispersive X-ray spectroscopy (SEM-EDX). The subsequent image analysis revealed C-rich particles with shapes that pointed to combustion processes. Moreover, carbonaceous particles seemed to act as vehicles for sulphur compounds and metals (S, Na, Fe, Ca, Mg, K, Al, Mn, Zn and Cu). Coarse particles were found to be mainly constituted by crustal material and marine and carbonaceous particles. Although most of the studied individual particles in PM10 samples (86.0%) had a diameter within the 0.1-2.5 µm range, 1.8% of them had sizes lower than 0.1 µm 40.2% of the total studied particles were estimated to be inhaled and deposited in the human respiratory tract; 12.3% of these particles would reach the deepest zones, thereby posing a major risk to human health.

Metallographic assessment of Al-12Si high-pressure die casting escalator steps.

A microstructural characterization study was performed on high-pressure die cast specimens extracted from escalator steps manufactured from an Al-12 wt.% Si alloy designed for structural applications. Black and white, color light optical imaging and scanning electron microscopy techniques were used to conduct the microstructural analysis. Most regions in the samples studied contained globular-rosette primary α-Al grains surrounded by an Al-Si eutectic aggregate, while primary dendritic α-Al grains were present in the surface layer. This dendritic microstructure was observed in the regions where the melt did not impinge directly on the die surface during cavity filling. Consequently, microstructures in the surface layer were nonuniform. Utilizing physical metallurgy principles, these results were analyzed in terms of the applied pressure and filling velocity during high-pressure die casting. The effects of these parameters on solidification at different locations of the casting are discussed.

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products.

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification's requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg2Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg2Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found.

Color metallography and electron microscopy techniques applied to the characterization of 413.0 aluminum alloys.

The influence on alloy 413.0 of the refinement and modification of its microstructure was analyzed by means of several microscopy techniques, as well as the effect of the application of high pressure during solidification. For each treatment and solidification pressure condition employed, the most suitable microscopy techniques for identifying and characterizing the phases present were investigated. Color metallography and electron microscopy techniques were applied to the qualitative microstructural analysis. Volume fraction and grain size of the primary α-Al were characterized by quantitative metallographic techniques. The results show that the effect caused by applying high pressure during solidification of the alloy is more pronounced than that caused by modification and refinement of the microstructure when it solidifies at atmospheric pressure. Furthermore, it has been shown that, for Al-Si alloy characterization, when aiming to characterize the primary α-Al phase, optical color metallography observed under crossed polarized light plus a sensitive tint filter is the most suitable technique. When the goal is to characterize the eutectic Si, the use of optical color metallography or electron microscopy is equally valid. The characterization of iron-rich intermetallic compounds should preferably be performed by means of backscattered electron imaging.

Microstructure investigations of streak formation in 6063 aluminum extrusions by optical metallographic techniques.

The present study investigates the effect of the solidification strategy for AA 6063 alloy on the surface appearance of anodized extrusions. The microstructure of the samples was analyzed using both light optical microscopy and scanning electron microscopy. Results show that if heavy segregation occurs from rapid solidification, coarse Mg2Si particles form, thus reducing the potential for precipitation strengthening by the finer ß-Mg2Si developed in the solid state. Differentially-strained regions formed during hot extrusion induce differences in particle size for magnesium silicide (Mg2Si) precipitates. Anodizing generates surface roughness due to Mg2Si particle dissolution and AlFeSi decohesion, which is related to both particle size and deformation. During anodizing, an oxide layer forms on the surface of the extruded products, which can lead to streak formation, usually a subject of rejection due to unacceptable heterogeneous reflectivity.