Source apportionment of the carcinogenic potential of polycyclic aromatic hydrocarbons (PAH) associated to airborne PM10 by a PMF model.

In order to perform a study of the carcinogenic potential of polycyclic aromatic hydrocarbons (PAH), benzo(a)pyrene equivalent (BaP-eq) concentration was calculated and modelled by a receptor model based on positive matrix factorization (PMF). Nineteen PAH associated to airborne PM10 of Zaragoza, Spain, were quantified during the sampling period 2001-2009 and used as potential variables by the PMF model. Afterwards, multiple linear regression analysis was used to quantify the potential sources of BaP-eq. Five sources were obtained as the optimal solution and vehicular emission was identified as the main carcinogenic source (35 %) followed by heavy-duty vehicles (28 %), light-oil combustion (18 %), natural gas (10 %) and coal combustion (9 %). Two of the most prevailing directions contributing to this carcinogenic character were the NE and N directions associated with a highway, industrial parks and a paper factory. The lifetime lung cancer risk exceeded the unit risk of 8.7 x 10(-5) per ng/m(3) BaP in both winter and autumn seasons and the most contributing source was the vehicular emission factor becoming an important issue in control strategies.

Influence of organic and inorganic markers in the source apportionment of airborne PM10 in Zaragoza (Spain) by two receptor models.

Improving knowledge on the apportionment of airborne particulate matter will be useful to handle and fulfill the legislation regarding this pollutant. The main aim of this work was to assess the influence of markers in the source apportionment of airborne PM10, in particular, whether the use of particle polycyclic aromatic hydrocarbon (PAH) and ions provided similar results to the ones obtained using not only the mentioned markers but also gas phase PAH and trace elements. In order to reach this aim, two receptor models: UNMIX and positive matrix factorization were applied to two sets of data in Zaragoza city from airborne PM10, a previously reported campaign (2003-2004) (Callén et al. Chemosphere 76:1120-1129, 2009), where PAH associated to the gas and particle phases, ions and trace elements were used as markers and a long sampling campaign (2001-2009), where only PAH in the particle phase and ions were analyzed. For both campaigns, positive matrix factorization was able to explain a higher number of sources than the UNMIX model. Independently of the sampling campaign and the receptor model used, soil resuspension was the main PM10 source, especially in the warm period (21st March-21st September), where most of the PM10 exceedances were produced. Despite some of the markers of anthropogenic sources were different for both campaigns, common sources associated to different combustion sources (coal, light-oil, heavier-oil, biomass, and traffic) were found and PAH in particle phase and ions seemed to be good markers for the airborne PM10 apportionment.

Nature and sources of particle associated polycyclic aromatic hydrocarbons (PAH) in the atmospheric environment of an urban area.

The total PAH associated to the airborne particulate matter (PM10) was apportioned by one receptor model based on positive matrix factorization (PMF) in an urban environment (Zaragoza city, Spain) during February 2010-January 2011. Four sources associated with coal combustion, gasoline, vehicular and stationary emissions were identified, allowing a good modelling of the total PAH (R(2) = 0.99). A seasonal behaviour of the four factors was obtained with higher concentrations in the cold season. The NE direction was one of the predominant directions showing the negative impact of industrial parks, a paper factory and a highway located in that direction. Samples were classified according to hierarchical cluster analysis obtaining that, episodes with the most negative impact on human health (the highest lifetime cancer risk concentrations), were produced by a higher contribution of stationary and vehicular emissions in winter season favoured by high relative humidity, low temperature and low wind speed.

Molecular simulation design of a multisite solid for the abatement of cold start emissions.

A highly effective hydrocarbon (HC) trap for the abatement of cold start HC emissions with specific adsorption sites for the different molecules present in the exhaust gases has been designed by means of molecular simulation tools, and later synthesized.

Apportionment of the airborne PM10 in Spain. Episodes of potential negative impact for human health.

The particulate matter with an aerodynamic diameter less than or equal to 10 and 2.5 microns respectively (PM10 and PM2.5) constitutes one of the main air pollutants, which is currently regulated in Europe through Directive 2008/50/EC due to its proven harmful effects on human health. In this paper, the airborne PM10 samples collected in Zaragoza city during 2001-2009 were apportioned by statistical tools based on principal component analysis with absolute principal component scores (PCA-APCS). PM10 samples were characterized regarding their concentrations of polycyclic aromatic hydrocarbons (PAH) and water-soluble ions. PAH were analyzed by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) and ions were analyzed by ion chromatography. A total of five factors were identified by PCA-APCS corresponding to different anthropogenic and natural sources. This work was focused on analyzing in more detail those samples involving higher negative impact on human health, in particular, PM10 samples exceeding the daily PM10 limit value of 50 µg m(-3) according to Directive 2008/50/EC and samples with concentrations of benzo[a]pyrene (BaP) higher than the upper assessment threshold (BaP > 0.6 ng m(-3)) established by the Directive 2004/107/EC. Most of the exceedances of the daily PM10 limit value were associated with direct and indirect North-African long-range transport. During these exceedances, it was observed that anthropogenic pollution sources slightly decreased with regard to the natural sources. This indicated that episodes of high PM10 could have a natural origin associated with long-range transport from the African continent. On the contrary, those exceedances with regional contribution and samples with BaP concentrations higher than 0.6 ng m(-3) showed an important contribution of anthropogenic pollution sources increasing their negative impact on human health.

Characterization of PM10-bound polycyclic aromatic hydrocarbons in the ambient air of Spanish urban and rural areas.

Urban areas constitute major pollution sources due to anthropogenic activities located in these areas. Among the legislated air pollutants, the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) and polycyclic aromatic hydrocarbons (PAH) are controlled under Directive 2008/50/EC and Directive 2004/107/EC, respectively due to their adverse health effects. A study was carried out at four urban and rural Spanish areas during the warm and cold seasons in 2008-2009 to quantify 19 PAH associated with the atmospheric PM10 by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) with the internal standard method. The particle-bound composition of the analysed PAH was 5 and 10 times greater in industrial and urban areas, respectively when compared to those measured in rural areas. The highest PAH concentrations during the cold period were possibly due to the additional contribution of domestic heating sources and meteorological conditions such as low temperature and solar irradiation. The use of molecular diagnostic ratios indicated that the possible, major PAH pollution sources in the most polluted areas were pyrogenic sources, mainly attributed to petroleum combustion sources (motor vehicle emissions and crude oil combustion). Petrogenic sources related to evaporative emissions also seemed to contribute in the most polluted area during the warm period. Those dates with high carcinogenic character according to the benzo(a)pyrene equivalent (BaP-eq) were also possibly attributed to petroleum combustion sources.

Waste tyre pyrolysis: modelling of a moving bed reactor.

This paper describes the development of a new model for waste tyre pyrolysis in a moving bed reactor. This model comprises three different sub-models: a kinetic sub-model that predicts solid conversion in terms of reaction time and temperature, a heat transfer sub-model that calculates the temperature profile inside the particle and the energy flux from the surroundings to the tyre particles and, finally, a hydrodynamic model that predicts the solid flow pattern inside the reactor. These three sub-models have been integrated in order to develop a comprehensive reactor model. Experimental results were obtained in a continuous moving bed reactor and used to validate model predictions, with good approximation achieved between the experimental and simulated results. In addition, a parametric study of the model was carried out, which showed that tyre particle heating is clearly faster than average particle residence time inside the reactor. Therefore, this fast particle heating together with fast reaction kinetics enables total solid conversion to be achieved in this system in accordance with the predictive model.

Seasonal variation of benzo(a)pyrene in the Spanish airborne PM10. Multivariate linear regression model applied to estimate BaP concentrations.

The estimation of benzo(a)pyrene (BaP) concentrations in ambient air is very important from an environmental point of view especially with the introduction of the Directive 2004/107/EC and due to the carcinogenic character of this pollutant. A sampling campaign of particulate matter less or equal than 10 microns (PM10) carried out during 2008-2009 in four locations of Spain was collected to determine experimentally BaP concentrations by gas chromatography mass-spectrometry mass-spectrometry (GC-MS-MS). Multivariate linear regression models (MLRM) were used to predict BaP air concentrations in two sampling places, taking PM10 and meteorological variables as possible predictors. The model obtained with data from two sampling sites (all sites model) (R(2)=0.817, PRESS/SSY=0.183) included the significant variables like PM10, temperature, solar radiation and wind speed and was internally and externally validated. The first validation was performed by cross validation and the last one by BaP concentrations from previous campaigns carried out in Zaragoza from 2001-2004. The proposed model constitutes a first approximation to estimate BaP concentrations in urban atmospheres with very good internal prediction (Q(CV)(2)=0.813, PRESS/SSY=0.187) and with the maximal external prediction for the 2001-2002 campaign (Q(ext)(2)=0.679 and PRESS/SSY=0.321) versus the 2001-2004 campaign (Q(ext)(2)=0.551, PRESS/SSY=0.449).

Valorisation of waste tyre by pyrolysis in a moving bed reactor.

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.

Comparison of receptor models for source apportionment of the PM10 in Zaragoza (Spain).

Receptor models are useful to understand the chemical and physical characteristics of air pollutants by identifying their sources and by estimating contributions of each source to receptor concentrations. In this work, three receptor models based on principal component analysis with absolute principal component scores (PCA-APCS), Unmix and positive matrix factorization (PMF) were applied to study for the first time the apportionment of the airborne particulate matter less or equal than 10microm (PM10) in Zaragoza, Spain, during 1year sampling campaign (2003-2004). The PM10 samples were characterized regarding their concentrations in inorganic components: trace elements and ions and also organic components: polycyclic aromatic hydrocarbons (PAH) not only in the solid phase but also in the gas phase. A comparison of the three receptor models was carried out in order to do a more robust characterization of the PM10. The three models predicted that the major sources of PM10 in Zaragoza were related to natural sources (60%, 75% and 47%, respectively, for PCA-APCS, Unmix and PMF) although anthropogenic sources also contributed to PM10 (28%, 25% and 39%). With regard to the anthropogenic sources, while PCA and PMF allowed high discrimination in the sources identification associated with different combustion sources such as traffic and industry, fossil fuel, biomass and fuel-oil combustion, heavy traffic and evaporative emissions, the Unmix model only allowed the identification of industry and traffic emissions, evaporative emissions and heavy-duty vehicles. The three models provided good correlations between the experimental and modelled PM10 concentrations with major precision and the closest agreement between the PMF and PCA models.

Some inferences on the mechanism of atmospheric gas/particle partitioning of polycyclic aromatic hydrocarbons (PAH) at Zaragoza (Spain).

Gas/particle partitioning of pollutants is an important mechanism determining atmospheric processing and its impact to environmental and human health. In this paper, the gas-particle partitioning of polycyclic aromatic hydrocarbons (PAH) has been studied with the aim of determining the main mechanism of PAH partitioning in Zaragoza (Spain) aerosols. To reach this goal, the ambient concentrations of PAH (gas and particle phase) collected in this city for one year period (2003-2004) have been analyzed. The partitioning between the particle and gas phases was studied according to three different models: the Junge adsorption model, the absorption into the organic matter model using the octanol-air (K(OA)) partition coefficient and the absorption into the organic matter plus the adsorption onto the soot carbon model using the soot-air (K(SA)) partition coefficients. Experimental gas/particle partition coefficients (K(P)) correlated well with the subcooled liquid vapour pressures (P(L)(0)) of PAH but with slopes higher than the expected value of -1. Experimental K(p) values were well fit to the modelled ones when, in addition to absorption into organic matter, adsorption onto the soot carbon was considered. It could be concluded that the main partition mechanism in Zaragoza aerosols was explained by adsorption onto the soot carbon. However, K(p) modelled values were affected by the different thermodynamic parameters related to soot types. The influence of the organic matter and elemental carbon fractions on the K(p) modelling was also studied. The different particle characteristics, local factors, the presence of non-exchangeable fraction and non-equilibrium were considered like main keys to explain deviations of the experimental K(p) values from predictions according to models.

Levels of selected metals in ambient air PM10 in an urban site of Zaragoza (Spain).

An assessment of the air quality of Zaragoza (Spain) was performed by determining the trace element content in airborne PM10 in a sampling campaign from July 2001 to July 2002. Samples were collected in a heavy traffic area with a high volume air sampler provided with a PM10 cutoff inlet. The levels of 16 elements (Al, Ba, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V, and Zn) were quantified after collecting the PM10 on Teflon-coated glass fiber filters (GFF). Regarding the PM10, 32% exceedance of the proposed PM10 daily limit was obtained, some of them corresponding to summer and autumn periods. The limit values of toxic trace elements from US-EPA, WHO, and EC were not exceeded, considering Zaragoza as a moderately polluted city under the current air quality guidelines. The contribution of anthropogenic sources to atmospheric elemental levels was reflected by the high values of enrichment factors for Zn, Pb, and Cu compared to the average crustal composition. Statistical analyses also determined the contribution of different sources to the PM10, finding that vehicle traffic and anthropogenic emissions related to combustion and industrial processes were the main pollutant sources as well as natural sources associated with transport of dust from Africa for specific dates. Regarding the influence of meteorological conditions on PM10 and trace elements concentrations, it was found that calm weather conditions with low wind speed favor the PM10 collection and the pollution for trace elements, suggesting the influence of local sources.

Three-ring PAH removal from waste hot gas by sorbents: influence of the sorbent characteristics.

Three-ring polycyclic aromatic hydrocarbons (PAH) are one of the most abundant PAH groups emitted during coal combustion. Four of them-acenaphthene (Ac), phenanthrene (Phe), fluorene (Fu), and anthracene (An)-have been listed by the U.S. EPA as priority pollutants. The aim in this paper is to study the abatement of this particular group of three-ring PAH from hot gas emissions during energy generation in coal combustion. The three-ring PAH adsorption capacities are related to the morphological and chemical properties of the 16 sorbents used in this work. Single and multiple linear regressions-principal component regression (PCR)-were applied in this study. The main conclusions reached are, first, that the micropore volume is the most determinant parameter for removal of these PAHs and, second, that the adsorption of three-ring PAH by sorbents from waste hot gas emissions is inversely proportional to their volatility: the lower the PAH volatility, the higher the adsorbent adsorption capacity. The adsorption isotherms show that Phe and An, both examples of PAH with three aromatic rings, behave similarly. However, their behavior differs from that of Ac and Fu, compounds in which only two of their three rings exhibit an aromatic nature.

Benzo(a)pyrene, benzo(a)anthracene, and dibenzo(a,h)anthracene emissions from coal and waste tire energy generation at atmospheric fluidized bed combustion (AFBC).

The main aim of this work was the analyzing of the release to the atmosphere of benzo[a]pyrene (BaP), dibenzo(a,h)anthracene (D(a,h)A), and benzo[a]anthracene (BaA), three of the most carcinogenic PAHs listed by US-EPA as priority pollutants, emitted from combustion at the last generation reactors used nowadays in power generation, fluidized bed reactors, trying to establish their incidence when waste materials are used as "new fuels". BaP, D(a,h)A, and BaA emissions, once collected in the sampling system, have been analyzed by fluorescence spectroscopy in the synchronous mode (FS) after extraction by ultrasonic bath with dimethylformamide (DMF) as solvent. Concerning to the combustion variables influence, the conclusion reached was that, in coal combustion, the lowest emissions of BaP are generated at percentages of excess oxygen of 20%, at flows corresponding to good fluidization conditions, 860 L/h (double of the minimum fluidization velocity) and temperatures out of 850 degrees C; the lowest emission of D(a,h)A are emitted at 20% excess oxygen, 900 L/h and out of 750 degrees C, and the lowest emission of BaA are generated at 20% excess oxygen, 860 L/h and out of the range 750-850 degrees C. Regarding tire as nonfossil fuel, higher emissions of BaP, BaA, and D(a,h)A are detected in comparison to coal combustion. In coal-tire blend, the BaP, BaA, and D(a,h)A emissions are more similar to the values obtained in coal combustion and not intermediate values as it could be expected by the blend composition.

Removal of naphthalene, phenanthrene, and pyrene by sorbents from hot gas.

It is the first time that the removal of polycyclic aromatic hydrocarbons (PAH) containing different aromatic rings number [naphthalene (Np), phenanthrene (Phe), and pyrene (Py)] from combustion hot gas has been carried out. The aim was to relate the sorbents textural characteristics with the adsorption capacity of these 2-4-ring PAH at the conditions emitted at energy generation. The sorbents textural parameters [total micropore volume (VN2), narrow micropore volume (VCO2), mesopore volume (VBJH), and the free active sites] were analyzed trying to correlate them with their Np, Phe, and Py adsorption capacities. To get this aim, single and multiple linear regressions (MLR) were applied to the three PAH. A principal component analysis was performed to generate new and uncorrelated variables. It enabled us to show that the relations between the textural parameters were analyzed using a principal components regression (PCR). The PCR analysis had a good statistical quality, but neither did it allow differentiating free active site types nor did VN2 and VCO2. The correlations were thus set up applying a MLR to the original variables. The regression statistical quality was similar to the PCR analysis, and it could give an easier explanation of the parameters that affected the adsorption. In Np adsorption, the 87% data variance was explained, and the adsorption was positively correlated to VCO2 and the micropore mean diameter (I.). In the Phe regression there was 98% variance explained, and its adsorption was positively correlated to the VN2 and the micropore distribution, n. Finally, in the Py adsorption, the 96% data variance was explained, and this adsorption was positively correlated to VN2 and VBJH. These dependencies were according to the molecular parameters of these compounds (molecular diameter and volatility) because the higher the number of aromatic rings of the PAH, the more favored the adsorbate-adsorbate interactions. Besides, the higher the mean diameter micropores, the lower the diffusional problems showed by Np, Phe, and Py.