Off-gassing from firefighter suits (nomex) as an indoor source of BTEXS.

The clothes and special equipment of firefighters can be a source of indoor air pollution. Nevertheless, it has not been investigated so far what the scale of the release of various compounds from such materials into the indoor air can be. The following study analysed the results of an experiment involving the passive measurement of concentrations of selected compounds, i.a. benzene, toluene, ethylbenzene, m,p-xylene, o-xylene, styrene, isopropylbenzene and n-propylbenzene (BTEXS) in the air of a room where firefighters' special clothing, which had been previously exposed to emissions from simulated fires, was stored. The study included simulations of fires involving three materials: wood, processed wood (OSB/fibreboard) and a mixture of plastics. After being exposed to the simulated fire environment, special clothing (so-called nomex) was placed in a sealed chamber, where passive collection of BTEXS was carried out using tube-type axial passive samplers and a gas chromatograph. Irrespective of which burned material special clothing was exposed to, the compound emitted into the air most intensively was toluene. Its rate of release from a single nomex ranges from 4.4 to 28.6 µg h-1, while the corresponding rates for the sum of BTEXS are between 9.97 and 44.29 µg h-1.

High concentrations of HgS, MeHg and toxic gas emissions in thermally affected waste dumps from hard coal mining in Poland.

This study aims to provide numerous environmental research approaches to understand the formation of mineral and organic mercury compounds in self-heating coal waste dumps of the Upper Silesian Coal Basin (USCB). The results are combined with environmental and health risk assessments. The mineralogy comprised accessory minerals in the fine fraction of thermally affected waste, i.e., Hg sulfides, most likely cinnabar or metacinnabar. Moreover, other metals, e.g., Pb, Zn and Cu, were found as sulfide forms. Apart from Hg, the ICP-ES/MS data confirmed the high content of Mn, Zn, Pb, Hg, Cr and Ba in these wastes. The high concentration of available Hg resulted in elevated MeHg concentrations in the dumps. There were no correlations or trends between MeHg concentrations and elemental Hg, TS, TOC, and pH. Furthermore, we did not detect microbial genes responsible for Hg methylation. The organic compounds identified in waste and emitted gases, such as organic acids, or free methyl radicals, common in such burn environments, could be responsible for the formation of MeHg. The concentration levels of gases, e.g., benzene, formaldehyde, NH3, emitted by the vents, reached or surpassed acceptable levels numerous times. The potential ecological and human health risks of these dumps were moderate to very high due to the significant influence of the high Hg concentrations.

Spatial and Temporal Volatility of PM2.5, PM10 and PM10-Bound B[a]P Concentrations and Assessment of the Exposure of the Population of Silesia in 2018-2021.

Air pollution both indoors and outdoors is a major cause of various diseases and premature deaths. Negative health effects are more frequently observed in a number of European countries characterized by significant pollution. In Poland, especially in Upper Silesia, the most serious problem is the high concentration of particulate matter (PM) and PM10-bound benzo[a]pyrene (B[a]P). The main source of these two pollutants is so-called "low emissions" associated with the burning of solid fuels mainly in domestic boilers and liquid fuels in road traffic. This study examined the variability in the PM and PM10-bound B[a]P concentrations and their relationships with meteorological parameters, i.e., atmospheric pressure, air temperature and wind speed, in 2018-2021 at 11 monitoring stations. In many Silesian cities, the average annual concentrations of PM10, PM2.5 and B[a]P were much higher than those recorded in other European countries. At each station, the average daily PM10 concentrations were exceeded on 12 to 126 days a year. Taking into account the WHO recommendation for PM2.5, the highest recorded average daily concentration exceeded the permissible level by almost 40 times. The same relationships were observed in all measurement years: PM10 concentrations were negatively correlated with air temperature (R = -0.386) and wind speed (R = -0.614). The highest concentrations were observed in the temperature range from -15 °C to -5 °C, when the wind speed did not exceed 0.5 m·s-1. The calculated lifetime cancer risk (LCR) associated with the exposure to B[a]P in the Silesian Voivodeship suggested 30-429 cases per 1 million people in the heating season depending on the scenario used for the calculations (IRIS, EPA or WHO).

Heavy metal- and organic-matter pollution due to self-heating coal-waste dumps in the Upper Silesian Coal Basin (Poland).

This study provides potential insight between self-heating coal-waste dumps and related environmental pollution in southern Poland. Samples collected from dumps in the Upper Silesian Coal Basin were used to quantify released contents of organic- and inorganic pollutants, i.e., polycyclic aromatic hydrocarbons (PAHs) and trace elements (Pb, Cd, Cr, Cu, Zn, Ni, Hg, As). Elevated Hg concentrations (~100-1078 mg/kg) and Pb (~600-2000 mg/kg) attest to the evaporation of these metals from deeper parts of the dumps. The acidic pH levels (3.0-4.5) may help to mobilize these elements. Pearson's correlation coefficients for samples analyzed by AAS and ICP-MS indicate a similar origin for Cd, Zn, and As. Mostly 2- and 3-ring PAHs, especially anthracene in burnt soil, dominate in the samples. Chlorinated PAHs, thiophenol, pyridines, quinolines (and derivatives) in thermally-altered samples, and waste containing pyrolytic bitumen indicate coking conditions. The high levels of Hg, Pb, and Cd, and chlorinated PAHs and nitrogen heterocycles formed or enriched during self-heating in these dumps should be deemed a significant environmental hazard. Calculating the lifetime cancer risks due to PAHs and heavy metals accumulations in the dumps are substantial, and access to these dumps should be prohibited.

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 vehicle's 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.

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.

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.

Concentration, origin and health hazard from fine particle-bound PAH at three characteristic sites in Southern Poland.

Suspended particles with the aerodynamic diameters not greater than 2.5 µm (PM2.5) and 1 µm (PM1, sub-fraction of PM2.5) were sampled at three sites: an urban background site, rural background site, and urban traffic site in southern Poland. In total, there were 240 samples taken within 02.08.2009-27.12.2010. Fifteen polycyclic aromatic hydrocarbons (PAH) were determined in each dust fraction. The averages of the concentration of total PAH (ΣPAH) and of particular PAH, as well as the share of carcinogenic PAH in total PAH (ΣPAHcarc/ΣPAH), carcinogenic equivalent, mutagenic equivalent, and TCDD-toxic equivalent appeared high compared to other areas in the world. Their high values express the significance of health hazard from PM and PM-bound PAH in southern Poland. The diagnostic ratios suggest that PM-bound PAH originate from municipal (PM1-2.5) and vehicular (PM1) combustion.