Source apportionment of suspended particulate matter (PM1, PM2.5 and PM10) collected in road and tram tunnels in Krakow, Poland.

Here, we present the results of a comprehensive study of air quality in two tunnels located in the city of Krakow, southern Poland. The study comprised three PM fractions of suspended particulate matter (PM1, PM2.5 and PM10) sampled during campaigns lasting from March 14 to April 24, 2016 and from June 28 to July 18, 2016, in the road tunnel and the tram tunnel, respectively. The collected samples had undergone comprehensive chemical, elemental and carbon isotope analyses. The results of these analyses gave the basis for better characterization of urban transport as a source of air pollution in the city. The concentrations of particulate matter varied, depending on the analysed PM fraction and the place of sampling. For the tram tunnel, the average concentrations were 53.2 µg·m-3 (PM1), 73.8 µg·m-3 (PM2.5), 96.5 µg·m-3 (PM10), to be compared with 44.2 µg·m-3, 137.7 µg·m-3, 221.5 µg·m-3, respectively, recorded in the road tunnel. The isotope-mass balance calculations carried out separately for the road and tram tunnel and for each PM fraction, revealed that 60 to 79% of carbon present in the samples collected in the road tunnel was associated with road transport, to be compared with 15-33% obtained in the tram tunnel. The second in importance were biogenic emissions (17-21% and 41-49% in the road and tram tunnel, respectively. Sixteen different polycyclic aromatic hydrocarbons (PAHs) have been identified in the analysed samples. As expected, much higher concentrations of PAHs were detected in the road tunnel when compared to the tram tunnel. Based on the analysed PAHs concentrations, health risk assessment was determined using 3 different types of indicators: carcinogenic equivalent (CEQ), mutagenic equivalent (MEQ) and toxic equivalent (TEQ).

Source attribution of carbonaceous fraction of particulate matter in the urban atmosphere based on chemical and carbon isotope composition.

Air quality is of large concern in the city of Krakow, southern Poland. A comprehensive study was launched by us in which two PM fractions (PM1 and PM10) were sampled during 1-year campaign, lasting from April 21, 2018 to March 19, 2019. A suite of modern analytical methods was used to characterize the chemical composition of the collected samples. The contents of 14 sugars, sugar alcohols and anhydrosugars, 16 polycyclic aromatic hydrocarbons, selected metals and non-metals and ions were analyzed, in addition to organic and elemental carbon content. The carbon isotope composition in both analysed PM fractions, combined with an isotope-mass balance method, allowed to distinguish three main components of carbonaceous emissions in the city: (1) emissions related to combustion of hard coal, (2) emissions related to road transport, and (3) biogenic emissions. The heating season emissions from coal combustion had the biggest contribution to the reservoir of carbonaceous aerosols in the PM10 fraction (44%) and, together with the biogenic emission, they were the biggest contributors to the PM1 fraction (41% and 44%, respectively). In the non-heating season, the dominant source of carbon in PM10 and PM1 fraction were the biogenic emissions (48 and 54%, respectively).

Comparison of concentrations of chemical species and emission sources PM2.5 before pandemic and during pandemic in Krakow, Poland.

Observations of air pollution in Krakow have shown that air quality has been improved during the last decade. In the presented study two factors affecting the physicochemical characteristic of PM2.5 fraction at AGH station in Krakow were observed. One is the ban of using solid fuels for heating purposes and the second is COVID-19 pandemic in Krakow. The PM2.5 fraction was collected during the whole year every 3rd day between 2nd March 2020 and 28th February 2021 at AGH station in Krakow. In total 110 PM2.5 fraction samples were collected. The chemical composition was determined for these samples. The elemental analysis was performed by energy dispersive X-ray fluorescence (EDXRF) technique, ions analysis was performed by ion chromatography (IC) and black carbon by optical method. In order to identify the emission sources the positive matrix factorization (PMF) was used. The results of such study were compared to similar analysis performed for PM2.5 for the period from June 2018 to May 2019 at AGH station in Krakow. The PM2.5 concentration dropped by 25% in 2020/2021 in comparison to 2018/2019 at this station. The concentrations of Si, K, Fe, Zn and Pb were lowering by 43-64% in the year 2020/2021 in comparison to 2018/2019. Cu, Mn, Zn and Pb come from mechanical abrasion of brakes and tires while Ti, Fe, Mn and Si are crustal species. They are the indicators of road dust (non-exhaust traffic source). Moreover, the annual average contribution of traffic/industrial/soil/construction work source was reduced in 2020/2021 in comparison to 2018/2019. As well the annual average contribution of fuels combustion was declining by 22% in 2020/2021 in comparison to 2018/2019. This study shows that the ban and lockdown, during COVID-19 pandemic, had significant impact on the characteristic of air pollution in Krakow.

Monocyte exposure to fine particulate matter results in miRNA release: A link between air pollution and potential clinical complication.

Chronic exposure to PM2.5 contributes to the pathogenesis of numerous disorders, although the underlying mechanisms remain unknown. The study investigated whether exposure of human monocytes to PM2.5 is associated with alterations in miRNAs. Monocytes were exposed in vitro to PM2.5 collected during winter and summer, followed by miRNA isolation from monocytes. Additionally, in 140 persons chronically exposed to air pollution, some miRNA patterns were isolated from serum seasonally. Between-season differences in chemical PM2.5 composition were observed. Some miRNAs were expressed both in monocytes and in human serum. MiR-34c-5p and miR-223-5p expression was more pronounced in winter. Bioinformatics analyses showed that selected miRNAs were involved in the regulation of several pathways. The expression of the same miRNA species in monocytes and serum suggests that these cells are involved in the production of miRNAs implicated in the development of disorders mediated by inflammation, oxidative stress, proliferation, and apoptosis after exposure to PM2.5.

Inter-laboratory comparison of ED-XRF/PIXE analytical techniques in the elemental analysis of filter-deposited multi-elemental certified reference materials representative of ambient particulate matter.

The quantification of the elemental concentration of ambient particulate matter is a challenging task because the observed elemental loadings are not well above the detection limit for most analytical techniques. Although non-destructive nuclear techniques are widely used for the chemical characterization of ambient aerosol, only one multi-element standard reference filter material that mimics ambient aerosol composition has become recently available in the market. To ensure accuracy, reliability and comparability of instruments performance, multiple reference materials with different elemental mass loadings are necessary. In this study, an intercomparison exercise was performed to evaluate the measurement uncertainty and instruments performance using multi-element dust standard reference samples deposited on PTFE filters. The filter samples, produced by means of dust dispersion, were tested in terms of homogeneity, reproducibility and long-term stability (≈40 months). Eight laboratories participated in the exercise. The evaluation of the results reported by the participants was performed by using two sets of reference values: a) the concentrations reported by the Expert Laboratory, b) the robust average concentrations reported by all participants. Most of the reported on the certificate of analysis elements were efficiently detected in the sample loadings prepared as representative for atmospheric samples by the Expert Laboratory. The average absolute relative difference between the reported and the reference values ranged between 0.1% (Ti) and 33.7% (Cr) (CRM-2584). The participants efficiently detected most of the elements except from the elements with atomic number lower than 16 (i.e. P, Al, Mg). The average absolute percentage difference between the participants results and the assigned value as derived by the expert laboratory was 17.5 ± 18.1% (CRM-2583; Cr, Pb excluded) and 16.7 ± 16.7% (CRM-2584; Cr, P excluded). The average "relative robust standard deviation" of the results reported by all participants was 25.1% (CRM-2583) and 22.8% (CRM-2584).

An analysis of the dust deposition on solar photovoltaic modules.

Solid particles impair the performance of the photovoltaic (PV) modules. This results in power losses which lower the efficiency of the system as well as the increases of temperature which additionally decreases the performance and lifetime. The deposited dust chemical composition, concentration and formation of a dust layer on the PV surface differ significantly in reference to time and location. In this study, an evaluation of dust deposition on the PV front cover glass during the non-heating season in one of the most polluted European cities, Kraków, was performed. The time-dependent particle deposition and its correlation to the air pollution with particulate matter were analysed. Dust deposited on several identical PV modules during variable exposure periods (from 1 day up to 1 week) and the samples of total suspended particles (TSP) on quartz fibre filters using a low volume sampler were collected during the non-heating season in the period of 5 weeks. The concentration of TSP in the study period ranged between 12.5 and 60.05 µg m-3 while the concentration of PM10 observed in the Voivodeship Inspectorate of Environmental Protection traffic station, located 1.2 km from the TSP sampler, ranged from 14 to 47 µg m-3. It was revealed that dust deposition density on a PV surface ranged from 7.5 to 42.1 mg m-2 for exposure periods of 1 day while the measured weekly dust deposition densities ranged from 25.8 to 277.0 mg m-2. The precipitation volume and its intensity as well as humidity significantly influence the deposited dust. The rate of dust accumulation reaches approximately 40 mg m-2day-1 in the no-precipitation period and it was at least two times higher than fluxes calculated on the basis of PM10 and TSP concentrations which suggest that additional forces such as electrostatic forces significantly influence dust deposition.

Seasonal contribution of assessed sources to submicron and fine particulate matter in a Central European urban area.

This study presents the air pollution findings of the submicron (PM1) and fine (PM2.5) particulate matter. The submicron particles are entirely absorbed by the human body and they cause the greatest health risk. For the PM2.5 concentration, there are yearly and/or daily limit values regulations by the European Union (EU) and World Health Organization (WHO). There are no such regulations for PM1 but for health risk reason the knowledge of its concentration is important. This paper presents the seasonal concentration contribution of PM1 and PM2.5, their chemical composition and assessed three basic sources. Daily samples of both fractions were collected from 2nd July 2016 to 27th February 2017 in Krakow, Poland. Apart from PM1 and PM2.5 the concentration of 16 elements, 8 ions and BC for each samples were measured. Based on these chemical species the positive matrix factorization (PMF) receptor modeling was used for the determination of three main sources contribution to the PM1 and PM2.5 concentrations. Daily average concentrations of PM2.5 were 12 µg/m3 in summer and 60 µg/m3 in winter. For PM1 it was 6.9 µg/m3 in summer and 17.3 µg/m3 in winter. These data show a significant difference in percentage contribution of PM1 in PM2.5 in summer (58%) and in winter (29%). For the combustion source, the concentrations calculated from PMF modeling in winter were 4.8 µg/m3 for PM1 and 31 µg/m3 for PM2.5. In summer, the concentrations were smaller than 1 µg/m3 for both fractions. Secondary aerosols' concentration for PM1 was 3.4 µg/m3 in summer and 11 µg/m3 in winter - for PM2.5 these were 7.1 µg/m3 and 17 µg/m3 respectively. The third source - soil, industry and traffic together, had small seasonal variation: for PM1 it was from 1.4 to 1.8 µg/m3 and for PM2.5 from 4.7 to 7.9 µg/m3.

Generation of hydroxyl radicals and singlet oxygen by particulate matter and its inorganic components.

Particulate matter (PM) can strongly affect redox biochemistry and therefore induce the response of the immune system and aggravate the course of autoimmune diseases. Nanoparticles containing transition metal compounds possessing semiconductor properties (TiO2, ZnO) may act as photocatalysts and accelerate the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). In this study, the NIST standard reference material, SRM 1648a, has been analyzed in terms of this consideration. Organic compounds present in SRM 1648a were removed by cold oxygen plasma treatment. Samples of SRM 1648a with removed organic content (<2% of organic carbon, <1% of nitrogen) were obtained within 2 h of this treatment. The treatment did not affect the morphology of the powder. The reference material and PM2.5 collected in Kraków are composed of smaller particles and nanoparticles forming aggregates. The efficiency of (photo)generation of hydroxyl radicals and singlet oxygen was compared for original and organics-free samples. The analyzed samples showed the highest activity towards ROS generation when exposed to UV-vis-NIR light, moderate under UV irradiation, and the lowest in dark. Data collected in the present study suggest that the organic fraction is mostly responsible for singlet oxygen generation, as almost twice higher efficiency of 1O2 generation was observed for the original NIST sample compared to the material without the organic fraction. However, particulate matter collected in Kraków was found to have a five times higher activity in singlet oxygen generation (compared for original NIST and Kraków dust samples).

Chemical content and estimated sources of fine fraction of particulate matter collected in Krakow.

The monitored level of pollution remains high in Krakow, Poland. Alerts regarding increased levels of pollution, which advise asthmatics, the elderly, and children to limit their exposure to open air, continue to be issued on numerous days. In this work, seasonal variations in PM2.5 (particulate matter containing particles with aerodynamic diameter no higher than 2.5 µm) concentrations are shown. An increasing trend is reported, which is enhanced during the colder seasons. The mean PM2.5 concentrations in Krakow exceeded the target value of 25 µg/m3 specified for 2015 in the spring, autumn, and winter seasons. For this reason, particulate matter pollution is of special concern. Elemental concentrations as well as the presence of black carbon (BC) and black smoke (BS) in PM2.5 samples were determined. Seasonal variations of Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Br, Rb, Sr, and Pb concentrations were observed whereas V, Cr, Ni, BC, and BS concentrations did not significantly change with the time of year. Seven factors were identified by the positive matrix factorization (PMF) technique, and one was non-identified. They were attributed to the following sources of pollution: steel industry, traffic (diesel exhaust), traffic (gasoline exhaust, brake wear), road dust, construction dust, combustion (biomass, coal), and non-ferrous metallurgical industry. The last, non-identified source, could be attributed to secondary aerosols. It is worth to mention that combustion shows significant seasonal variations with a high impact in winter. The reported results of the completed studies may significantly aid in solving air quality issues in the city by highlighting major sources of air pollution.

Quantitative Assessment of PM2.5 Sources and Their Seasonal Variation in Krakow.

In industry areas of Poland such as Silesia or urban sites like Krakow and some other cities, the levels of pollutants frequently breach air quality standards. Particulate matter (PM) is the most important constituent of atmospheric pollution. Beginning on 1st February 2014 until 31st January 2015, the samples of fine particulate matter PM2.5 (aerodynamic diameter of particles less than or equal to 2.5 µm) were collected at a site in the south-eastern Krakow urban background area. During this period, 194 samples were taken. The samples showed daily variation of PM2.5 concentration. From these data, monthly variations were estimated and presented in this paper. Monthly integrated data are more representative for the Krakow urban background and show seasonal variation of PM2.5 pollution. The lowest monthly concentration value was found for August 2014-about 10 µg m-3, the highest for February 2014-70 µg m-3, whereas the average annual value was about 31 µg/m3. Utilizing X-ray fluorescence method, concentrations of 15 elements for each sample were determined and 8 inorganic ions were analyzed by ion chromatography. Additionally, the samples were analyzed for black carbon (BC). Receptor model PMF (positive matrix factorization) was used for source identification and apportionment. The modeling identified six sources and their quantitative contributions to PM2.5 total mass. The following sources were identified: combustion, secondary nitrate and sulfate, biomass burning, industry or/and soil and traffic. Finally, monthly variations of each source are presented.

Chemical composition of submicron and fine particulate matter collected in Krakow, Poland. Consequences for the APARIC project.

Submicron particulate matter containing particles with an aerodynamic diameter ≤1 µm (PM1) are not monitored continuously by Environmental Protection Agencies around the World and are seldom studied. Numerous studies have indicated that people exposed to ultrafine (≤100 nm), submicron and fine particulate matter containing particles with an aerodynamic diameter ≤2.5 µm (PM2.5), can suffer from respiratory track diseases, cardiovascular, immunological or heart diseases and others. Inorganic pollutants containing redox active transition metals and small gaseous molecules, are involved in the generation of reactive oxygen and reactive nitrogen species. Inhalation of this kind of particles can affect immune-toxicity. Environmental pollution may aggravate the course of autoimmune diseases, in particular influence the mechanisms of the autoimmune system. Important factors that influence the toxicity of particulate matter, are particle size distribution, composition and concentration. This report deals with the composition of PM1 and PM2.5 fractions collected in Krakow, Poland. In spring 2015, the mean concentrations of PM1 and PM2.5 were 19 ± 14 and 27 ± 19 µg/m3, respectively. The PM2.5 fraction contained approximately 70 ± 17% of submicron particulate matter. In spring 2016, the mean concentrations of PM1 and PM2.5 were 12 ± 5 and 22 ± 12 µg/m3, respectively. The PM2.5 fraction contained approximately 60 ± 15% of submicron particulate matter. The concentrations of the elements Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr and Pb in both fractions were determined by X-ray fluorescence spectrometry. Most of the analyzed metals had higher concentrations in the fine fraction than in the submicron one. Concentrations of V and As were below the detection limit in both fractions, whereas concentrations of Mn and Ca were below the detection limits in the PM1 fraction. The results are discussed in terms of the consequences they may have on the APARIC project presently underway in Krakow.

Overall human mortality and morbidity due to exposure to air pollution.

OBJECTIVES: Concentrations of particulate matter that contains particles with diameter ≤ 10 mm (PM10) and diameter ≤ 2.5 mm (PM2.5) as well as nitrogen dioxide (NO2) have considerable impact on human mortality, especially in the cases when cardiovascular or respiratory causes are attributed. Additionally, they affect morbidity. An estimation of human mortality and morbidity due to the increased concentrations of PM10, PM2.5 and NO2 between the years 2005-2013 was performed for the city of Kraków, Poland. For this purpose the Air Quality Health Impact Assessment Tool (AirQ) software was successfully applied. MATERIAL AND METHODS: The Air Quality Health Impact Assessment Tool was used for the calculation of the total, cardiovascular and respiratory mortality as well as hospital admissions related to cardiovascular and respiratory diseases. Data on concentrations of PM10, PM2.5 and NO2, which was obtained from the website of the Voivodeship Inspectorate for Environmental Protection (WIOS) in Kraków, was used in this study. RESULTS: Total mortality due to exposure to PM10 in 2005 was found to be 41 deaths per 100 000 and dropped to 30 deaths per 100 000 in 2013. Cardiovascular mortality was 2 times lower than the total mortality. However, hospital admissions due to respiratory diseases were more than an order of magnitude higher than the respiratory mortality. CONCLUSIONS: The calculated total mortality due to PM2.5 was higher than that due to PM10. Air pollution was determined to have a significant effect on human health. The values obtained by the use of the AirQ software for the city of Kraków imply that exposure to polluted air can result in serious health problems.

LabVIEW control software for scanning micro-beam X-ray fluorescence spectrometer.

Confocal micro-beam X-ray fluorescence microscope was constructed. The system was assembled from commercially available components - a low power X-ray tube source, polycapillary X-ray optics and silicon drift detector - controlled by an in-house developed LabVIEW software. A video camera coupled to optical microscope was utilized to display the area excited by X-ray beam. The camera image calibration and scan area definition software were also based entirely on LabVIEW code. Presently, the main area of application of the newly constructed spectrometer is 2-dimensional mapping of element distribution in environmental, biological and geological samples with micrometer spatial resolution. The hardware and the developed software can already handle volumetric 3-D confocal scans. In this work, a front panel graphical user interface as well as communication protocols between hardware components were described. Two applications of the spectrometer, to homogeneity testing of titanium layers and to imaging of various types of grains in air particulate matter collected on membrane filters, were presented.

Elemental and ionic concentrations in the urban aerosol in Antwerp, Belgium.

The results of a study of the elemental and ionic composition of the ambient aerosol in and around Antwerp are presented. Four sampling campaigns were performed, covering all seasons. The samples were obtained by filtration and impaction methods. Subsequently, the filters were analyzed by X-ray fluorescence spectrometry for elements, and the impactor substrates were leached with water and analyzed by ion chromatography for ions. When comparing the results of the chemical analysis with the meteorological information, it was found that the concentration of certain elements and ions in aerosol samples was affected considerably by the location of the sampling site and by the meteorological conditions. In relatively less polluted places like small towns and rural regions around Antwerp, the concentrations of some elements and ions showed qualitatively a positive or negative correlation in their time variations with the amount of precipitation. Hence, we suppose that in the first case these elements and ions are contained mainly in the more hygroscopic fraction (the most apparent is the behavior of Na and Cl), and that in the second case, the elements are mainly present in the less hygroscopic fraction of the ambient aerosol. However, this behavior of the elements and ions may be different for various particle size ranges. In the highly urbanized and industrial sites close to the central and industrial parts of Antwerp, these correlations were not found. This could be connected with the high and variable local aerosol generation rate, when only heavy rains are able to provide a sufficient removal of the aerosols from the atmosphere.