Indoor PM from residential coal combustion: Levels, chemical composition, and toxicity.

Indoor air quality is crucial for human health due to the significant time people spend at home, and it is mainly affected by internal sources such as solid fuel combustion for heating. This study investigated the indoor air quality and health implications associated with residential coal burning covering gaseous pollutants (CO, CO2 and total volatile organic compounds), particulate matter, and toxicity. The PM10 chemical composition was obtained by ICP-MS/OES (elements), ion chromatography (water-soluble ions) and thermal-optical analysis (organic and elemental carbon). During coal combustion, PM10 levels were higher (up to 8.8 times) than background levels and the indoor-to-outdoor ratios were, on average, greater than unity, confirming the existence of a significant indoor source. The chemical characterisation of PM10 revealed increased concentrations of organic carbon and elemental carbon during coal combustion as well as arsenic, cadmium and lead. Carcinogenic risks associated with exposure to arsenic exceeded safety thresholds. Indoor air quality fluctuated during the study, with varying toxicity levels assessed using the Aliivibrio fischeri bioluminescence inhibition assay. These findings underscore the importance of mitigating indoor air pollution associated with coal burning and highlight the potential health risks from long-term exposure. Effective interventions are needed to improve indoor air quality and reduce health risks in coal-burning households.

Insights on the combination of off-line and on-line measurement approaches for source apportionment studies.

This paper presents a source apportionment study performed on a dataset collected at a trafficked site in Coimbra (Portugal) during the period December 2018-June 2019. The novelty of this work consists in the methodological approach used and the sensitivity study carried out to give hints to potential future applications. Indeed, a multi-time resolution and multi-parameter study was performed joining together aerosol data from 24-h chemically characterized samples and high-time resolution multi-wavelength absorption coefficients retrieved by an Aethalometer. A detailed sensitivity study on the most suitable combination of time resolution and uncertainties was carried out to obtain reliable physical and stable solutions over all analyses. In parallel, a regular EPA-PMF source apportionment study using chemical and optical variables averaged on 24 h is presented and discussed in comparison to the more complex multi-time and multi-parameter approach. Apart from results pertaining to the identification and relevance of different sources in Coimbra, the methodological results shown here can give guidance for readers who want to implement optical variables jointly with chemical ones in the same model run.

Toxicological and Mutagenic Effects of Particulate Matter from Domestic Activities.

People spend most of their time indoors, particularly in their houses where daily activities are carried out, enhancing particulate matter (PM) emissions with consequent adverse health impacts. This study intended to appraise the toxicological and mutagenic responses of particulate matter with a diameter less than 10 µm (PM10) released from cooking and ironing activities under different conditions. The cytotoxicity of the PM10 total organic extracts was tested in A549 cells using the WST-8 and the lactate dehydrogenase (LDH) assays, while the interference in cell cycle dynamics and reactive oxygen species (ROS) production was analysed by flow cytometry. The S. typhimurium TA98 and TA100 Ames tester strains with and without metabolic activation were employed to determine the mutagenic potential of the PM10-bound polycyclic aromatic hydrocarbons (PAHs). PM10 organic extracts decreased the metabolic activity of A549 cells; however, no effects in the LDH release were observed. An increase in ROS levels was registered only for cells treated with PM10 at IC20 from steam ironing, in low ventilation conditions, while cell cycle dynamics was only affected by exposure to PM10 at IC20 from frying horse mackerel and grilling boneless pork strips. No mutagenic effects were observed for all the PM10-bound PAHs samples.

In vitro toxicity of particulate matter emissions from residential pellet combustion.

Particulate matter emissions (PM10) from the combustion, in a residential stove, of two commercial brands of certified (ENplus A1) pellets, a non-certified brand and laboratory made pellets of acacia were tested for their ability to induce ecotoxic, cytotoxic, and mutagenic responses in unicellular organisms and a human cell line. Ecotoxicity was evaluated through the Vibrio fischeri bioluminescence inhibition assay. Moreover, cytotoxicity was assessed at two time points (24- and 48-hr) through two complementary techniques in order to evaluate the cellular metabolic activity and membrane integrity of human lung epithelial cells A549. The Ames test using two Salmonella typhimurium strains (TA100 and TA98) was employed to assess the mutagenic potential of the polycyclic aromatic hydrocarbon fraction extracted from the PM10 samples. Results obtained with the bioluminescent bacteria indicated that only particles from the combustion of acacia pellets were toxic. All samples induced impairment on the A549 cells metabolic activity, while no significant release of lactate dehydrogenase was recorded. PM10 emissions from acacia pellets were the most cytotoxic, while samples from both certified pellets evoked significant cytotoxicity at lower doses. Cytotoxicity time-dependency was only observed for PM10 from the combustion of acacia pellets and one of the brands of certified pellets. Mutagenic activity was not detected in both S. typhimurium strains. This study emphasises the role of the raw material for pellet manufacturing on the toxicological profile of PM emissions. Alternative raw materials should be deeply investigated before their use in pelletisation and combustion in residential appliances.

Lung-deposited dose of particulate matter from residential exposure to smoke from wood burning.

Residential settings are of utmost importance for human exposure, as it is where people spend most of their time. Residential wood combustion is a widespread practice known as a source of indoor particulate matter (PM). Nevertheless, research on the risks of exposure associated with this source is scarce, and a better understanding of respiratory deposition of smoke particles is needed. The dosimetry model ExDoM2 was applied to determine the deposited dose of inhalable particulate matter (PM10) from residential biomass combustion in the human respiratory tract (HRT) of adults and children. The dose was estimated using PM10 exposure concentrations obtained from a field campaign carried out in two households during the operation of an open fireplace and a woodstove. Simultaneously, PM10 levels were monitored outside to investigate the outdoor dose in a rural area strongly impacted by biomass burning emissions. Indoors, the 8-h average PM10 concentrations ranged from 88.3 to 489 µg m-3 and from 69.4 to 122 µg m-3 for the operation of the fireplace and the woodstove, respectively, while outdoor average PM10 concentrations ranged from 17.3 to 94.2 µg m-3. The highest amount of the deposited particles was recorded in the extrathoracic region (68-79%), whereas the deposition was much lower in the tracheobronchial tree (5-6%) and alveolar-interstitial region (16-21%). The total dose received while using the fireplace was more than twofold the one received in the room with a woodstove and more than 10 times higher than in the absence of the source. Overall, indoor doses were higher than the ones received by a subject exposed outdoors, especially at the alveolar-interstitial region. After 24 h of exposure, it was estimated that approximately 35 to 37% of the particles deposited in the HRT were transferred to the gastrointestinal tract, while approximately 2.0-2.5% were absorbed into the blood. The results from exposure and dose of indoor particles gathered in this work suggest that homeowners should be encouraged to upgrade the wood burning technology to reduce the PM levels inside their residences. This study also provides biologically relevant results on the lung deposition of particles from residential biomass burning that can be used as a reference for future research.

Fingerprinting and emission rates of particulate organic compounds from typical restaurants in Portugal.

The aim of this study was a detailed chemical characterisation of the particles released during the preparation of popular Portuguese dishes. PM2.5 samples were collected from the exhaust stacks on the roofs of a university canteen, a charcoal-grilled chicken restaurant and a wood-oven roasted piglet restaurant. The speciation of organic compounds was carried out by gas chromatography-mass spectrometry. The canteen was responsible for the lowest emissions of PM2.5, while emissions from the roasted piglet restaurant were the highest. Naphthalene was quantified as the most abundant aromatic compound in particle emissions from the canteen, while phenanthrene, fluoranthene, pyrene and chrysene were the dominant polycyclic aromatic hydrocarbons in samples from the other establishments. Benzo[a]pyrene equivalent concentrations obtained for the charcoal-grilled chicken and piglet restaurant indicate a dangerous carcinogenic potential to human health. Cholesterol was the prevalent sterol. Its highest values were obtained in particles from the charcoal-grilled chicken restaurant (621 ± 233 µg g-1 PM2.5). Oleic and palmitoleic were the unsaturated fatty acids identified at highest concentrations (from trace levels to 34.4 and to 6.89 mg g-1 PM2.5, respectively). Resin acids, such as dehydroabietic and abietic, were detected in all samples from the wood-oven roasted piglet restaurant. Nicotinamide was the amide detected at highest amount in emissions from the university canteen during the preparation of stews (7.67 mg g-1 PM2.5). Levoglucosan and its isomers were identified in all samples from the roasted piglet restaurant, but only the first monosaccharide anhydride was present in emissions from the university canteen and the charcoal-grilled chicken restaurant. Additionally, emission rates were estimated for the most representative compounds, taking into account the specific activity of each restaurant.

In vitro toxicity of indoor and outdoor PM10 from residential wood combustion.

Particulate matter with aerodynamic diameter < 10 µm (PM10) was collected, indoors and outdoors, when wood burning appliances (open fireplace and woodstove) were in operation. The PM10 ecotoxicity was assessed with the Vibrio fischeri bioluminescence inhibition assay, while the cytotoxicity was evaluated by the WST-8 and lactate dehydrogenase (LDH) release assays using A549 cells. Extracts of PM10-bound polycyclic aromatic hydrocarbons (PAH) were tested for their mutagenicity through the TA98 and TA100 Ames test. The bioluminescent inhibition assay revealed that indoor particles released from the fireplace were the most toxic. Indoors, the reduction in A549 cell metabolic activity was over two times higher for the fireplace in comparison with the woodstove (32 ± 3.2% and 72 ± 7.6% at the highest dose, respectively). Indoor particles from the fireplace were found to induce greater cytotoxicity than the corresponding outdoor samples. Combined WST-8 and LDH results suggest that PM10 exposure induce apoptotic cell death pathway in which the cell membrane integrity is maintained. Indoor and outdoor samples lacked direct and indirect mutagenic activity in any of the tester strains. For indoor-generated PM10, organic carbon and PAH were significantly correlated with cell viability and bioluminescence reduction, suggesting a role of organic compounds in toxicity.

Cooking activities in a domestic kitchen: Chemical and toxicological profiling of emissions.

To obtain emission factors and cooking-related chemical signatures, a monitoring campaign was carried out in a modern kitchen where different dishes of the Latin cuisine were prepared. Particulate matter (PM10, PM2.5 and PM1) and total volatile organic compounds (TVOCs) were continuously measured. Passive tubes for carbonyls and a high volume PM10 sampler were simultaneously used. PM10 filters were analysed for organic and elemental carbon and for multiple organic compounds, including polyaromatic hydrocarbons (PAHs). The toxic potential of PM10 was evaluated using a bioluminescence inhibition bioassay. Acrolein was never detected, while formaldehyde and acetaldehyde levels were comparable to those in the background air. The protection limit for TVOCs was always exceeded. Fine particles comprised more than 86% of the PM10 mass concentrations. PM10 emission rates ranged from 124 to 369 µg min-1. Relatively low PAH concentrations were obtained. PM10 encompassed alcohols, acids, plasticisers, alkyl esters, sterols, sugars, polyols, glyceridic compounds, phenolics, among others. Total concentrations were 1.9-5.3 times higher during cooking than in the background air but, for some compounds, differences of tens or hundreds of times were registered. PM10 from grilled pork was found to contribute to non-negligible cancer risks and to be very toxic, while samples from other dishes were categorised as toxic.

Loadings, chemical patterns and risks of inhalable road dust particles in an Atlantic city in the north of Portugal.

Road dust resuspension has a significant contribution to the atmospheric particulate matter levels in urban areas, but loadings, emission factors, and chemical source profiles vary geographically, hampering the accuracy of emission inventories and source contribution estimates. Given the dearth of studies on the variability of road dust, in the present study, an in-situ resuspension chamber was used to collect PM10 samples from seven representative streets in Viana do Castelo, the northernmost coastal city in Portugal. PM10 samples were analysed for organic and elemental carbon by a thermo-optical technique, elemental composition by ICP-MS and ICP-AES, and organic constituents by GC-MS. Emission factors were estimated to be, on average, 340 and 41.2 mg veh-1 km-1 for cobbled and asphalt pavements, respectively. Organic carbon accounted for 5.56 ± 1.24% of the PM10 mass. Very low concentrations of PAHs and their alkylated congeners were detected, denoting a slight predominance of petrogenic compounds. Si, Al, Fe, Ca and K were the most abundant elements. The calculation of various geochemical indices (enrichment factor, geoaccumulation index, pollution index and potential ecological risk) showed that road dust was extremely enriched and contaminated by elements from tyre and brake wear (e.g. Sb, Sn, Cu, Bi and Zn), while lithophile elements showed no enrichment. For As, the geochemical and pollution indices reached their maximum in the street most influenced by agricultural activities. Sb, Cd, Cu and As can pose a very high ecological risk. Sb can be regarded as the pollutant of highest concern, since it represented 57% of the total ecological risk. Hazard indices higher than 1 for some anthropogenic elements indicate that non-carcinogenic effects may occur. Except for a street with more severe braking, the total carcinogenic risks can be considered insignificant.

Mineralogical, chemical and leaching characteristics of ashes from residential biomass combustion.

Four types of pellets and three agro-fuels were chemically characterised and burned in a pellet stove. To assess the influence of the material composing the firebox and the combustion efficiency of distinct biomass heating devices in the composition of the bottom ashes, three of the pellets were also burned in a conventional woodstove and in a fireplace. Ashes were analysed for their C, H and N contents by an elemental analyser, whilst major and trace elements were quantified by inductively coupled plasma atomic-emission spectrometry and inductively coupled plasma mass spectrometry, respectively. The mineralogy of ashes was determined by X-ray powder diffraction. The European standard test was applied to samples to determine the leaching potential of major, minor and trace elements. The contents of major and trace elements in the different types of biomass presented enormous variations, which are reflected in dissimilar mineralogical and chemical compositions of the respective ashes. The leachable potential of several elements of environmental concern present in oxy-anionic form at the alkaline pH of biomass ashes were generally high in all samples. Concentrations of some elements in the leachates were in the range of values with classification of "hazardous materials" by the European legislation in what respects the acceptance of these wastes at landfills. Pellets made up of wood wastes and containing preservatives (chromated copper arsenate and ammoniacal copper arsenate) are of concern. Due to lower combustion efficiencies, the leachable potential for most of the trace elements in ashes from the woodstove, and especially from the fireplace, was lower than that of the pellet stove.

Polycyclic aromatic hydrocarbons and their derivatives (nitro-PAHs, oxygenated PAHs, and azaarenes) in PM2.5 from Southern European cities.

Atmospheric particulate matter (PM2.5) samples were collected over two one month periods during winter and summer in three Southern European cities (Oporto - traffic site, Florence - urban background, Athens - suburban). Concentrations of 27 polycyclic aromatic hydrocarbons (PAHs), 15 nitro-PAHs (NPAHs), 15 oxygenated-PAHs (OPAHs) and 4 azaarenes (AZAs) were determined. On average, the winter-summer concentrations of ΣPAHs were 16.3-5.60, 7.75-3.02 and 3.44-0.658ngm-3 in Oporto, Florence and Athens, respectively. The corresponding concentrations of ΣNPAHs were 15.8-9.15, 10.9-3.36 and 15.9-2.73ngm-3, whilst ΣOPAHs varied in the ranges 41.8-19.0, 11.3-3.10 and 12.6-0.704ngm-3. Concentrations of ΣAZAs were always below 0.5ngm-3. Irrespective of the city, the dominant PAHs were benzo[b+j+k]fluoranthene, retene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene. The most abundant OPAH in all cities was 1,8-naphthalic anhydride, whereas 5-nitroacenaphthene was the prevailing NPAH. The ΣOPAHs/ΣPAHs and ΣNPAHs/ΣPAHs were higher in summer than in winter, suggesting increasing formation of derivatives by photochemical degradation of PAHs. Molecular diagnostic ratios suggested that, after traffic, biomass burning was the dominant emission source. Apart from being influenced by seasonal sources, the marked differences between winter and summer may indicate that these diagnostic ratios are particularly sensitive to photodegradation, and thus should be applied and interpreted cautiously. The lifetime excess cancer risk from inhalation was, in part, attributable to PAH derivatives, acclaiming the need to include these compounds in regular monitoring programmes. On average, 206, 88 and 26 cancer cases per million people were estimated, by the World Health Organisation method, for the traffic-impacted, urban background and suburban atmospheres of Oporto, Florence and Athens, respectively.

Mutagenicity assessment of aerosols in emissions from domestic combustion processes.

Domestic biofuel combustion is one of the major sources of regional and local air pollution, mainly regarding particulate matter and organic compounds, during winter periods. Mutagenic and carcinogenic activity potentials of the ambient particulate matter have been associated with the fraction of polycyclic aromatic hydrocarbons (PAH) and their oxygenated (OPAH) and nitrogenated (NPAH) derivatives. This study aimed at assessing the mutagenicity potential of the fraction of this polycyclic aromatic compound in particles (PM10) from domestic combustion by using the Ames assays with Salmonella typhimurium TA98 and TA100. Seven biofuels, including four types of pellets and three agro-fuels (olive pit, almond shell and shell of pine nuts), were tested in an automatic pellet stove, and two types of wood (Pinus pinaster, maritime pine, and Eucalyptus globulus, eucalypt) were burned in a traditional wood stove. For this latter appliance, two combustion phases­Devolatilisation and flaming/smouldering­Were characterised separately. A direct-acting mutagenic effect for the devolatilisation phase of pine combustion and for both phases of eucalypt combustion was found. Almond shell revealed a weak direct-acting mutagenic effect, while one type of pellets, made of recycled wastes, and pine (devolatilisation) presented a cytotoxic effect towards strain TA100. Compared to the manually fired appliance, the automatic pellet stove promoted lower polyaromatic mutagenic emissions. For this device, only two of the studied biofuels presented a weak mutagenic or cytotoxic potential.

Mutagenicity assessment of aerosols in emissions from domestic combustion processes.

Domestic biofuel combustion is one of the major sources of regional and local air pollution, mainly regarding particulate matter and organic compounds, during winter periods. Mutagenic and carcinogenic activity potentials of the ambient particulate matter have been associated with the fraction of polycyclic aromatic hydrocarbons (PAH) and their oxygenated (OPAH) and nitrogenated (NPAH) derivatives. This study aimed at assessing the mutagenicity potential of the fraction of this polycyclic aromatic compound in particles (PM10) from domestic combustion by using the Ames assays with Salmonella typhimurium TA98 and TA100. Seven biofuels, including four types of pellets and three agro-fuels (olive pit, almond shell and shell of pine nuts), were tested in an automatic pellet stove, and two types of wood (Pinus pinaster, maritime pine, and Eucalyptus globulus, eucalypt) were burned in a traditional wood stove. For this latter appliance, two combustion phases-devolatilisation and flaming/smouldering-were characterised separately. A direct-acting mutagenic effect for the devolatilisation phase of pine combustion and for both phases of eucalypt combustion was found. Almond shell revealed a weak direct-acting mutagenic effect, while one type of pellets, made of recycled wastes, and pine (devolatilisation) presented a cytotoxic effect towards strain TA100. Compared to the manually fired appliance, the automatic pellet stove promoted lower polyaromatic mutagenic emissions. For this device, only two of the studied biofuels presented a weak mutagenic or cytotoxic potential.

Factors controlling air quality in different European subway systems.

Sampling campaigns using the same equipment and methodology were conducted to assess and compare the air quality at three South European subway systems (Barcelona, Athens and Oporto), focusing on concentrations and chemical composition of PM2.5 on subway platforms, as well as PM2.5 concentrations inside trains. Experimental results showed that the mean PM2.5 concentrations widely varied among the European subway systems, and even among different platforms within the same underground system, which might be associated to distinct station and tunnel designs and ventilation systems. In all cases PM2.5 concentrations on the platforms were higher than those in the urban ambient air, evidencing that there is generation of PM2.5 associated with the subway systems operation. Subway PM2.5 consisted of elemental iron, total carbon, crustal matter, secondary inorganic compounds, insoluble sulphate, halite and trace elements. Of all metals, Fe was the most abundant, accounting for 29-43% of the total PM2.5 mass (41-61% if Fe2O3 is considered), indicating the existence of an Fe source in the subway system, which could have its origin in mechanical friction and wear processes between rails, wheels and brakes. The trace elements with the highest enrichment in the subway PM2.5 were Ba, Cu, Mn, Zn, Cr, Sb, Sr, Ni, Sn, Co, Zr and Mo. Similar PM2.5 diurnal trends were observed on platforms from different subway systems, with higher concentrations during subway operating hours than during the transport service interruption, and lower levels on weekends than on weekdays. PM2.5 concentrations depended largely on the operation and frequency of the trains and the ventilation system, and were lower inside the trains, when air conditioning system was operating properly, than on the platforms. However, the PM2.5 concentrations increased considerably when the train windows were open. The PM2.5 levels inside the trains decreased with the trains passage in aboveground sections.

Elements and polycyclic aromatic hydrocarbons in exhaust particles emitted by light-duty vehicles.

The main purpose of this work was to evaluate the chemical composition of particulate matter (PM) emitted by eight different light-duty vehicles. Exhaust samples from petrol and diesel cars (Euro 3 to Euro 5) were collected in a chassis dynamometer facility. To simulate the real-world driving conditions, three ARTEMIS cycles were followed: road, to simulate a fluid traffic flow and urban with hot and cold starts, to simulate driving conditions in cities. Samples were analysed for the water-soluble ions, for the elemental composition and for polycyclic aromatic hydrocarbons (PAHs), respectively, by ion chromatography, inductively coupled plasma atomic emission spectroscopy (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and gas chromatography-mass spectrometry (GC-MS). Nitrate and phosphate were the major water-soluble ions in the exhaust particles emitted from diesel and petrol vehicles, respectively. The amount of material emitted is affected by the vehicle age. For vehicles ≥Euro 4, most elements were below the detection limits. Sodium, with emission factors in the ranges 23.5-62.4 and 78.2-227µg km(-1), for petrol and diesel Euro 3 vehicles, respectively, was the major element. The emission factors of metallic elements indicated that diesel vehicles release three to five times more than petrol automobiles. Element emissions under urban cycles are higher than those found for on-road driving, being three or four times higher, for petrol vehicles, and two or three times, for diesel vehicles. The difference between cycles is mainly due to the high emissions for the urban cycle with hot start-up. As registered for elements, most of the PAH emissions for vehicles ≥Euro 4 were also below the detection limits. Regardless of the vehicle models or driving cycles, the two- to four-ring PAHs were always dominant. Naphthalene, with emission factors up to 925 µg km(-1), was always the most abundant PAH. The relative cancer risk associated with naphthalene was estimated to be up to several orders of magnitude higher than any of the chemical species found in the PM phase. The highest PAH emission factors were registered for diesel-powered vehicles. The condition of the vehicle can exert a decisive influence on both element and PAH emissions.

Emission of trace gases and organic components in smoke particles from a wildfire in a mixed-evergreen forest in Portugal.

On May 2009, both the gas and particulate fractions of smoke from a wildfire in Sever do Vouga, central Portugal, were sampled. Total hydrocarbons and carbon oxides (CO(2) and CO) were measured using automatic analysers with flame ionisation and non-dispersive infrared detectors, respectively. Fine (PM(2.5)) and coarse (PM(2.5-10)) particles from the smoke plume were analysed by a thermal-optical transmission technique to determine the elemental and organic carbon (EC and OC) content. Subsequently, the particle samples were solvent extracted and fractionated by vacuum flash chromatography into different classes of organic compounds. The detailed organic speciation was performed by gas chromatography-mass spectrometry. The CO, CO(2) and total hydrocarbon emission factors (g kg(-1) dry fuel) were 170 ± 83, 1485 ± 147, and 9.8 ± 0.90, respectively. It was observed that the particulate matter and OC emissions are significantly enhanced under smouldering fire conditions. The aerosol emissions were dominated by fine particles whose mass was mainly composed of organic constituents, such as degradation products from biopolymers (e.g. levoglucosan from cellulose, methoxyphenols from lignin). The compound classes also included homologous series (n-alkanes, n-alkenes, n-alkanoic acids and n-alkanols), monosaccharide derivatives from cellulose, steroid and terpenoid biomarkers, and polycyclic aromatic hydrocarbons (PAHs). The most abundant PAH was retene. Even carbon number homologs of monoglycerides were identified for the first time as biomarkers in biomass burning aerosols.