Barbara Kozielska

Hazardous Compounds in Urban Pm in the Central Part of Upper Silesia (Poland) in Winter

Abstract Thirteen fractions of ambient dust were investigated in Zabrze, a typical urban area in the central part of Upper Silesia (Poland), during a heating season. Fifteen PAH and Cr, Mn, Co, Ni, As, Se, Cd, Pb contents of each fraction were determined. The dust was sampled with use of a cascade impactor and chemically analyzed with an energy dispersive X-ray fluorescence spectrometer (PANalytical Epsilon 5) and a gas chromatograph with a flame ionisation detector (Perkin Elmer Clarus 500). The concentrations of PM1 and the PM1-related PAH and elements were much higher than the ones of the coarse dust (PM2.5-10) and the substances contained in it. The concentrations of total PAH and carcinogenic PAH were very high (the concentrations of PM1-, PM2.5-, and PM10-related BaP were 16.08, 19.19, 19.32 ng m-3, respectively). The municipal emission, resulted mainly from hard coal combustion processes, appeared to be the main factor affecting the air quality in Zabrze in winter.

Traffic emission effects on ambient air pollution by PM2.5-related PAH in Upper Silesia, Poland

The ambient concentration of particle-bound polycyclic aromatic hydrocarbons (PAHs) was investigated in two industrial towns in Upper Silesia, Poland. The 24 h samples of PM2.5 (particles with aerodynamic diameter ≤ 2.5 µm) were collected simultaneously at busy roads (or crossroads) and at an urban background site. Additionally, the samples were collected during the heaviest traffic density (rush hours, from 8 am to 6 pm) at the five crossroads with the most traffic in Zabrze. The impact of traffic emission resulted in the specific distribution of particular PAH concentrations, PAH groups and diagnostic ratio values for all sampling points. The emission of diesel engine cars was significant and influenced dust and PAH concentrations. At four crossroads (including one at which the measurements were carried out for 24 h), the PAH profiles corresponded to that observed for gasoline engine exhausts. At the crossroad in Zabrze, the road in Ruda Śląska and urban area backgrounds without for traffic emission, the concentration of PM2.5 and PM-related PAHs can be affected by hard coal, wood and crude oil combustion.

POLYCYCLIC AROMATIC HYDROCARBONS IN DUST EMITTED FROM STOKER - FIRED BOILERS

In the present paper, results of investigations of Polycyclic Aromatic Hydrocarbons (PAHs) in granulometric fractions of dust, emitted from 9 hard coal fired mechanic stoker boilers, are presented. Exhaust gases were sampled with a Mark III dust sampler. Extracts derived from the dust fractions were analysed by using Gas Chromatography (GC). The 16 PAHs, total PAHs and equivalent benzo(a)pyrene (B(a)P) were determined. Results of measurements averaged over all examined boilers are presented as concentrations, contents and contributions of investigated hydrocarbons to particular standardised fractions of dust classified according to particle sizes. Distributions of PAHs and their profiles in the dust fractions were determined. The emission factors for B(a)P and Toxic Equivalent B(a)P (TE B(a)P) were determined and proved to be several times higher than for pulverised fuel fired boilers. In the emitted dust, 73% of the total PAHs most hazardous to human health are comprised in PM1.

Submicron particle-bound polycyclic aromatic hydrocarbons in the Polish teaching rooms: Concentrations, origin and health hazard

The goal of the work was to investigate the concentrations of the 16 US EPA priority polycyclic aromatic hydrocarbons (PAH) bound to submicrometer particles (particulate matter, PM1) suspended in the air of university teaching rooms and in the atmospheric air outside. Two teaching rooms were selected in two Polish cities, Gliwice, southern Poland, and Warsaw, central Poland, differing with regard to the ambient concentrations and major sources of PM and PAH. The variabilities of indoor and outdoor 24-hr concentrations of PM1-bound PAH, the ratio (I/O) of the indoor to outdoor 24-hr concentrations of PM1-bound PAH, probable sources of PAH and the level of the hazard from the mixture of the 16 PAH (ΣPAH) to humans at both sites were analyzed. In both Warsaw and Gliwice, the mean concentrations of PM1-bound ΣPAH were slightly higher in the atmospheric air than in the rooms. The indoor and outdoor concentrations of individual PAH in Gliwice were correlated, in Warsaw - they were not. Most probably, the lack of the correlations in Warsaw was due to the existence of an unidentified indoor source of gaseous PAH enriching PM1 in phenanthrene, fluorene, and pyrene. Although the ambient concentrations of PM1-bound PAH were low compared to the ones observed earlier at both sites, they were much higher than in other urbanized European areas. However, because of low mass share of heavy PAH in ΣPAH, the various indicators of the health hazard from the 16 PAH mixture were low compared to other regions.

Geochemical markers and polycyclic aromatic hydrocarbons in solvent extracts from diesel engine particulate matter

Exhaust particulate from compression ignition (CI) engines running on engine and chassis dynamometers was studied. Particulate dichloromethane extracts were qualitatively and quantitatively analyzed for polycyclic aromatic hydrocarbons (PAHs) and biomarkers by gas chromatography with flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS). PAH group profiles were made and the PAH group shares according to the number of rings (2 or 3; 4; 5 or more) as well as diagnostic indices were calculated. Values of geochemical ratios of selected biomarkers and alkyl aromatic hydrocarbons were compared with literature values. A geochemical interpretation was carried out using these values and biomarker and alkyl aromatic hydrocarbon distributions. It has been shown that geochemical features are unequivocally connected to the emission of fossil fuels and biofuels burned in CI engines. The effect of the exothermic combustion process is limited to low-molecular-weight compounds, which shows that the applied methodology permits source identification of PAHs coexisting in the particulate emitted.

Sources of organic pollution in particulate matter and soil of Silesian Agglomeration (Poland): evidence from geochemical markers.

The exact input of particular sources to polycyclic aromatic hydrocarbons (PAHs) concentrations in urban and industrial agglomerations is still not well recognized. The major breakthrough is possible using geochemical markers. In the air aerosol and soil samples from areas located in the direct influence of industry/traffic in Silesian Agglomeration (Poland), PAHs and other organic compounds were analyzed, including geochemical markers (biomarkers) and polar compounds from fossil fuels and biomass. Gas chromatography (GC-FID) and gas chromatography–mass spectrometry (GC–MS) were applied to investigate the composition of particulate matter and soil extracts. The results suggest that the predominant source of PAHs is fossil fuel. The presence and distribution of steranes, pentacyclic triterpenoids (i.e., hopanes and moretanes) and alkyl PAHs point to traffic emissions and fossil fuel combustion, mainly bituminous coal for power and heat purposes, as the main source of PAHs in the region. Moreover, the presence of fossil fuel biomarker in particulate matter and soil extracts from a rural site, previously considered to be free of organic pollution, requires a cautious interpretation for PAHs results. Apart from the fossil fuel, also other sources of contamination were identified in particulate matter extracts by their markers: phenols and levoglucosan for biomass and diisopropylnaphthalenes for printing materials combustion. The absence of polar biomass combustion indicators in soil extracts might be related to their higher reactivity.

OCCURRENCE OF POLYCYCLIC AROMATIC HYDROCARBONS IN DUST EMITTED FROM CIRCULATING FLUIDIZED BED BOILERS

Abstract Occurrence of polycyclic aromatic hydrocarbons (PAHs) in granulometric fractions of dust emitted from a hard coal fired circulating fluidized bed (CFB) boiler was investigated. The dust was sampled with the use of a Mark III impactor. In each fraction of dust, by using gas chromatography (GC), 16 selected PAHs and total PAHs were determined and the toxic equivalent B(a)P (TE B(a)P) was computed. The results, recalculated for the standard granulometric fractions, are presented as concentrations and content of the determined PAHs in dust. Distributions of PAHs and their profiles in the granulometric dust fractions were studied also. The PAHs in dust emitted from the CFB boiler were compared with those emitted from mechanical grate boilers; a distinctly lower content of PAHs was found in dust emitted from the former.

Distribution of coal and coal combustion related organic pollutants in the environment of the Upper Silesian Industrial Region

In this study, a large sample set (276) was separated into up to 15 groups, including coal, fly ash, total particulate matter, coal wastes, river sediments, and different water types. Grouping the sample set into these categories helped to identify the typical features of combustion or water-washing and compare them using newly developed polycyclic aromatic hydrocarbon diagnostic ratios. A wide range of organic pollutants were identified in samples, including aromatic and polycyclic hydrocarbons, nitrogen-heterocycles, sulphur-heterocycles + trithiolane, and polycyclic aromatic hydrocarbons substituted with oxygen functional groups. The distribution of compounds was significantly influenced by water washing or combustion. During the self-heating of coal wastes, secondary compounds such as chlorinated aromatics (chlorobenzene, chloroanthracene, etc.) or light sulphur compounds (e.g. benzenethiol and benzo[b]thiophene) were formed (synthesised). Since these compounds are generally absent in sedimentary organic matter, their origin may be connected with high-temperature formation in burning coal dumps. These compounds should be identified as persistent organic pollutants (POPs) in the environment. The newly defined diagnostic ratios have worked well in separating samples (petrogenic and pyrogenic) and have pointed out the effect of incomplete combustion on self-heated coal waste, ash from domestic furnaces, or water washing and biodegradation of the studied compounds.

Occurrence of organic phosphates in particulate matter of the vehicle exhausts and outdoor environment – A case study

The occurrence and concentrations of a wide range of organic phosphates (OPEs) in vehicles exhaust (VPM), ambient air particulate matter (APM), and soil of various urban environments were researched. VPM comes from passenger cars, commercial vehicles, marine and bus engines emitted in New European Driving Cycle tests whereas APM was sampled in several sites of the Upper Silesia region (Poland). APM and VPM collected on filters and soil from the same locations as APM sampling sites were extracted with dichloromethane and extracts analyzed by gas chromatography-mass spectrometry. The OPEs found include aryl phosphates such as triphenyl phosphate (TPhP) and tricresyl phosphate (TCP), alkyl phosphates - triethyl phosphate (TEP), tripropyl phosphate (TPP), tributyl phosphate (TBP) and tri(butoxyethyl)phosphate (TBEP), and alkylchlorinated phosphates including tris-(2-chloroisopropyl) phosphate (TCiPP) and tris(2-chloroethyl) phosphate (TCEP). Occurrence and concentrations of these compounds in the PM investigated are highly variable. It was found that total concentrations in APM are directly related to traffic density in particular sites of the urban environment and a style of a vehicle driving. The highest emission of OPEs was found at a crossroad and city center sites where traffic is the densest and vehicles stops and starts are frequent. Village and residential areas were less exposed to OPEs emission. Since OPEs concentrations show exponential correlations to each other also human exposure to these compounds increases exponentially with increasing traffic density. High TEP and TBP level is tentatively proposed as an indicator of emission from petrol-fueled cars. Concentrations of OPEs in some soil are related to their emission to the air and resistance to degradation of a particular compound since only the most resistant TCiPP and TPhP were identified in soil extracts.

POLYCYCLIC AROMATIC HYDROCARBONS IN VARIOUS FRANCTIONS OF AMBIENT PARTICULATE MATTER AT AREAS DOMINATED BY TRAFFIC EMISSION

The paper presents the results of the research of 16 polycyclic aromatic hydrocarbons (PAHs) associated with four fractions of particulate matter (PM, PM10, PM2,5 and PM1; fractions of particles whose aerodynamic diameter ranges from 30 nm to respectively: 100, 10, 2.5 and 1 μm) conducted at points located on the side of a highway and at a busy crossroads in Katowice. The highway research was carried out in the spring, and the crossroads research in the summer of 2012. Samples were taken by low pressure impactor DEKATI. The analysis of PAHs in ambient particulate matter samples was performed by gas chromatography. The average concentration of the sum of 16 PAH associated with PM, which amounted to 14.6 ng/m3 in the spring, was two times higher than in the summer. This concentration was a few or even several times lower than the levels recorded earlier in the cities of southern Poland in the winter. Meanwhile, indicators of toxicity, mutagenicity and carcinogenicity calculated for PAH at the highway and the crossroads were high. This indicates high health risk generated by the presence of PAHs in the Katowice air also in spring and summer time. The values of diagnostic ratio, roughly showing the origin of PAHs associated with the PM, confirmed that during the period of the research transportation was the main source of PAHs in both points of Katowice.