Seasonal Variability of PM10 Chemical Composition Including 1,3,5-triphenylbenzene, Marker of Plastic Combustion and Toxicity in Wadowice, South Poland

ABSTRACT The objective of this research was to evaluate the seasonal variation of the chemical composition of PM10 including polycyclic aromatic hydrocarbons (PAHs) and 1,3,5-triphenylbenzene (135TPB), which is a well known marker of plastic combustion. The presented work is a part of the project concerning assessment of air quality of small cities around Krakow agglomeration. Monitoring campaign was conducted between February and October 2017 in Wadowice, a small city in Krakow agglomeration, South Poland. To widen the knowledge of Krakow's agglomeration air quality, other aerosol chemical components were analyzed. Ion chromatography (IC) was used for analysis of cations and anions, while gas chromatography-mass spectrometry (GC-MS) was used for PAHs. Samples were also analyzed for OC/EC (organic/elemental carbon) by thermal-optical analysis with a Sunset Laboratory carbon analyzer, Sunset Inc. The co-combustion of plastic in addition to conventional fuels and the respective impact on air quality is evaluated via the concentration of the marker compound 135TPB. Co-combustion of plastics with fuels resulted in a higher abundance of fluorene and most of 4–6 ring PAHs, in agreement with recent literature. Authors proved that other sources besides plastic burning, including road transport, residential heating, residential combustion, industrial emissions, affect the air quality in South Poland. The modeling tool Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT), developed by NOAA's Air Resources Laboratory, was used to define the possible areas outside Wadowice contributing to urban air pollution

Particulate matter and odor emission factors from small scale biomass combustion units

Zsfassung in dt. SpracheEmissionen aus Biomasseverbrennung bestehen aus hunderten gasförmigen und partikulären Verbindungen. Die Emissionen hängen dabei stark von den existierenden Verbrennungstechnologien ab, die zu umweltfreundlichen Lösungen weiter entwickelt werden müssen. Ebenso werden für die Immisionsinventuren verlässliche Datensätze benötigt um realistische Szenarien für Emissionsreduktionen zu entwickeln. Aufgrund der Bedeutung von heimischen Holzarten im Hausbrandsektor befasst sich diese Studie mit einer umfangreichen Erfassung der Emissionen aus der Verbrennung von 12 mitteleuropäischen Holzarten, sowie von Holz-Briketts in einem modernen Kaminofen. Die Brennstoffauswahl wurde noch durch Pellets ergänzt, die in einem automatischen Pelletofen verbrannt wurden.Für jede Brennstoffart wurden Partikel- und Gasemissionsfaktoren bestimmt. Von den mit einer speziellen Verdünnungsapparatur gesammelten PM2.5 und PM10 Proben wurden umfangreiche "chemische Profile" ermittelt.Zusätzlich wurden Geruchsmessungen in Abgas vorgenommen. Der Geruch von Holzrauch wurde bis jetzt nur selten als Problem betrachtet, obwohl dieser auf die Anwesenheit von anderen, potentiell toxischen Schadstoffen im Holzrauch hindeutet. Aus dem Verhältnis von Geruchseinheiten und PM10 der Emissionsmessung wurde abgeleitet, dass bei einem Auftreten von 30 µg m-³ PM10 von Holzrauch in der Außenluft mit einer Geruchswahrnehmung zu rechnen ist.Diese Bedingungen werden insbesondere in besiedelten alpinen Tallagen in der Heizperiode oft erreicht. Die gasförmigen Emissionen mit Ausnahme von NOx lagen beim Pelletofen am niedrigsten. Geruch war beim Betrieb der Pelletsverbrennung Betrieb nicht nachweisbar. Die PM10 Emissionen waren gering, jedoch vergleichbar mit den niedrig emittierenden Holzarten aus den Kaminofen-Experimenten. Die Mehrzahl der Holzarten weisen aber etwa die 10-fache PM10 Emission im Vergleich zu den Pellets auf.Die Emissionen der als Marker für die Holzrauchverbrennung angewendeten Verbindungen wiesen deutlich unterschiedliche Muster auf, im Vergleich zu Emissionen von "traditionellen Öfen". Trotz der hohen Variabilität des "diagnostischen Verhältnisses" von PM10 und Levoglucosan, konnte ein charakteristisches Verhältnis für den Kaminofen abgeleitet werden.Ebenso unterschied sich das Levoglucosan/Mannosan Verhältnis für Hartholz von jenem der "traditionellen Öfen", während das Verhältnis für Weichholz robust, vergleichbar für sehr unterschiedliche Ofentypen war.Die im Experiment verwendeten modernen Öfen, emittierten mehr polycyklische aromatische Kohlenwasserstoffe (PAKs) als es erwartet. Mit Hilfe eines multilinearen Regressionsmodells konnte gezeigt werden, dass die BaP Emissionen durch die Input-Variablen "Abbrandgeschwindigkeit" und "EC Emissionen" abgeleitet werden können. Rasche Abbrände mit hohen Verbrennungstemperaturen bewirken relativ höhere EC-Emissionen, gekoppelt mit einer höheren PAK Bildung. Dieses Ergebnis ist erheblicher Bedeutung, da Holzrauch einen großen Anteil and der Emission von PAKs in vielen europäischen Ländern hat. Um am Sektor der Emissionen der Biomasseverbrennung insbesondere den Feinstaub zu verringern werden Ofentauschprogramme durchgeführt. Diese Studie zeigt nun, dass die Emissionsreduktion bei Umstieg von "alter" auf "neue" Technologien für PAH und Ruß in deutlich geringerem Ausmaß ausfällt, als bei Feinstaub. Die bedeutet, dass der EU - Grenzwert für BaP von 1 ng m-³ als Jahresmittelwert in der Außenluft in jenen Regionen, in welchen bereits hohe Werte auftreten, nicht einfach durch Ofentauschprogramme reduziert werden kann, bzw. in Regionen, in welchen ein Umstieg von fossilen Brennstoffen (Gas, Heizöl-EL) auf Biomasse-Feuerungen mit Zunahmen der BaP Belastung gerechnet werden muss.Wood burning is a significant source of particulate matter (PM) in Europe, especially in the cold season. Comprehensive knowledge of wood burning emissions may help to evaluate the existing technologies and to develop environmentally friendlier solutions, applicable for local societies. On the other hand it is important from emission inventories' point of view to work with updated emission profiles in order to obtain reliable scenarios and plan adequate strategies for reducing the pollution levels. Therefore this work offers an exhaustive study on emissions from burning of 12 Central European wood types, wood pellets, briquettes and garden waste in two popular, modern stoves. Additionally a measurement of odor emissions was conducted to assess the possible impact of wood smoke odor nuisance in Mid European countries. Concerning the findings of this study it was derived that already for an ambient wood smoke concentration of 30 µg m-³, the odor could be recognized. It was also predicted that the short-term odor nuisance may be significant, especially in mountain valleys, where wood smoke could be trapped by the temperature inversion for longer time and short term local concentrations might occur several times higher than the average. Lowest gas emissions were observed for the automatically fired pellet heater. Also no odor was detected in exhaust samples from pellets burning. PM levels for the pellet stove were similar to those obtained for lowest emitting wood types. The "high emitters" among wood logs reached levels an order of magnitude higher than pellets. The substances recognized as unique wood burning tracers and applied for source apportionment studies were found in significant concentrations. The levoglucosan/mannosan ratios were stable and higher for hardwood fuels than observed from a tiled stove. The levoglucosan/PM ratio showed a much larger variation. It was observed, that the emission of tracer compounds from wood types considered here, are influenced by batch-to-batch variations (e.g. wood types from a wood species exhibiting widely different combustion properties within a test series and between studies under comparison.The modern stoves used in the experiment, emitted considerable amounts of toxic Polycyclic Aromatic Hydrocarbons (PAHs).The BaP/PM ratios were variable and were shown to depend strongly on the burn rate. Applying a multiple linear regression model it was possible to explain the BaP/PM10 emission ratio with high quality of fit including the burn rate and elemental carbon (EC) as input parameters. Wood burning emissions are an extremely prominent source of BaP in the ambient air and the use of small stoves increases significantly the threat of exceeding the threshold limit of BaP (in the European Union 1 ng m-³ annual average). The study shows that flue gas from modern small scale heating systems could contain elevated BaP concentrations (with emissions higher by a factor of 10 for high burn rate combustion). Thus, a stove change program might reduce the PM emission but will not be not be likewise effective reducing the PAH emissions.17

Solvent effects on extraction of polycyclic aromatic hydrocarbons in ambient aerosol samples

Polycyclic Aromatic Hydrocarbons (PAHs) in the ambient particulate matter pose one of the most important issues in the focus of environmental management. The concentration of their representative, Benzo(a)pyrene (BaP), undergoes limitations according to European Union directive. However, a successful control over the pollution levels and their sources is limited by the high uncertainty of analytical and statistical approaches used for their characterization. Here we compare differences in PAH concentrations related to the use of different solvents in the course of ultrasonic extraction of a certified reference material (PM10-like PAH mixture) and filter samples of ambient particulate matter collected in Austria for the CG-MS PAH analysis. Using solvents of increasing polarity: Cyclohexane (0,006), Toluene (0,099), Dichloromethane (0,309), Acetone (0,43) and Acetonitrile (0,460), as well as mixtures of those, filters representing high and low concentrations of particulate matter were investigated. Although some scatter of the obtained concentrations was observed no trend related to the polarity of the solvent became visible. Regarding the reproducibility, which can be expected of PAH analysis no significant difference between the different solvents was determined. This result is valid for all compounds under investigation

Solvent effects on extraction of polycyclic aromatic hydrocarbons in ambient aerosol samples

Polycyclic Aromatic Hydrocarbons (PAHs) in the ambient particulate matter pose one of the most important issues in the focus of environmental management. The concentration of their representative, Benzo(a)pyrene (BaP), undergoes limitations according to European Union directive. However, a successful control over the pollution levels and their sources is limited by the high uncertainty of analytical and statistical approaches used for their characterization. Here we compare differences in PAH concentrations related to the use of different solvents in the course of ultrasonic extraction of a certified reference material (PM10-like PAH mixture) and filter samples of ambient particulate matter collected in Austria for the CG-MS PAH analysis. Using solvents of increasing polarity: Cyclohexane (0,006), Toluene (0,099), Dichloromethane (0,309), Acetone (0,43) and Acetonitrile (0,460), as well as mixtures of those, filters representing high and low concentrations of particulate matter were investigated. Although some scatter of the obtained concentrations was observed no trend related to the polarity of the solvent became visible. Regarding the reproducibility, which can be expected of PAH analysis no significant difference between the different solvents was determined. This result is valid for all compounds under investigation

Solvent effects on extraction of polycyclic aromatic hydrocarbons in ambient aerosol samples

Polycyclic Aromatic Hydrocarbons (PAHs) in the ambient particulate matter pose one of the most important issues in the focus of environmental management. The concentration of their representative, Benzo(a)pyrene (BaP), undergoes limitations according to European Union directive. However, a successful control over the pollution levels and their sources is limited by the high uncertainty of analytical and statistical approaches used for their characterization. Here we compare differences in PAH concentrations related to the use of different solvents in the course of ultrasonic extraction of a certified reference material (PM10-like PAH mixture) and filter samples of ambient particulate matter collected in Austria for the CG-MS PAH analysis. Using solvents of increasing polarity: Cyclohexane (0,006), Toluene (0,099), Dichloromethane (0,309), Acetone (0,43) and Acetonitrile (0,460), as well as mixtures of those, filters representing high and low concentrations of particulate matter were investigated. Although some scatter of the obtained concentrations was observed no trend related to the polarity of the solvent became visible. Regarding the reproducibility, which can be expected of PAH analysis no significant difference between the different solvents was determined. This result is valid for all compounds under investigation

Carbonaceous species in atmospheric aerosols from the Krakow area (Malopolska District): carbonaceous species dry deposition analysis

Organic and elemental carbon content in PM10 was studied at three sites in Malopolska District representing the city centre (Krakow), rural/residential (Bialka) and residential/industrial environments (Krakow). The PM10 samples were collected during the winter time study. The highest concentrations of carbonaceous species were observed in Skawina (36.9 μg·m-3 of OC and 9.6 μg·m-3 of EC). The lowest OC and EC concentrations were reported in Krakow (15.2 μg·m-3 and 3.9 μg·m-3, respectively. The highest concentration of carbonaceous species and the highest wind velocities in Skawina influenced the highest values of the dry deposition fluxes. Correlations between OC, EC and chemical constituents and meteorological parameters suggest that a) Krakow was influenced by local emission sources and temperature inversion occurrence; b) Bialka was under the influence of local emission sources and long-range transport of particles; c) Skawina was impacted by local emission sources

Carbonaceous species in atmospheric aerosols from the Krakow area (Malopolska District): carbonaceous species dry deposition analysis

Organic and elemental carbon content in PM10 was studied at three sites in Malopolska District representing the city centre (Krakow), rural/residential (Bialka) and residential/industrial environments (Krakow). The PM10 samples were collected during the winter time study. The highest concentrations of carbonaceous species were observed in Skawina (36.9 μg·m-3 of OC and 9.6 μg·m-3 of EC). The lowest OC and EC concentrations were reported in Krakow (15.2 μg·m-3 and 3.9 μg·m-3, respectively. The highest concentration of carbonaceous species and the highest wind velocities in Skawina influenced the highest values of the dry deposition fluxes. Correlations between OC, EC and chemical constituents and meteorological parameters suggest that a) Krakow was influenced by local emission sources and temperature inversion occurrence; b) Bialka was under the influence of local emission sources and long-range transport of particles; c) Skawina was impacted by local emission sources

Polycyclic aromatic hydrocarbons (PAHs) associated with PM10 collected in Wadowice, South Poland

Krakow is a city in southern Poland inhabited by about 741,000 people. However, Krakow’s agglomeration includes neighboring cities, hence more than 1 million people live there. The agglomeration is struggling with the problem of air pollution. In 2016, admissible average annual concentrations of PM10 (40 μg / m3) were exceeded at all measuring points. Furthermore, daily PM10 concentrations were regularly exceeded in the winter, which is associated with increased coal combustion during this period. Fortunately, interest in the subject of air quality in the world is constantly growing. People are more often aware of the negative impact on health of chemical compounds present in particulate matter (PM) such as Polycyclic Aromatic Hydrocarbons (PAHs), which were proved to be cancerogenic and mutagenic for people. That is why it is so important to study their presence in the ambient air. PM10 collected in the center of Wadowice (22.12.2016 – 13.10.2017) were investigated. PAHs were extracted from particulate matter and analysed applying the GC/MS technique. The results are discussed in the article