María Soledad Callén

Spatial and temporal PAH concentrations in Zaragoza, Spain

The concentration of seven polycyclic aromatic hydrocarbons (PAH) associated with the atmospheric solid phase was measured in the Zaragoza (North-East of Spain) atmosphere using fluorescence spectroscopy in the synchronous mode (FS). The PAH results were reported for four different urban and suburban places, located within the city and during the period October 1999-September 2001. The PAH data obtained indicated the importance of local sources generated from urban/industrial areas. Although the PAH total concentration was quite similar in all the sampling sites, the main differences were due to Benzo[a]pyrene (BaP) and Coronene (Cor) concentrations, reaching the highest values in the sites associated with heavy traffic (trucks, lorries, etc.). The temporal evolution of atmospheric solid phase PAH concentrations indicated a seasonal trend. Higher PAH concentrations were found during colder seasons for the four sampling sites. The influence of environmental parameters such as temperature, rain, relative humidity, wind speed and direction on the PAH emissions was analyzed observing a positive correlation between the total PAH concentration and the relative humidity and a negative one with the temperature. With regard to the wind direction, higher PAH emissions were detected when wind was coming from an east and north-east direction. Wind from a north-westerly direction showed lower PAH emissions associated with the cierzo wind which provided cleaner air.

Source apportionment of atmospheric PM2.5-bound polycyclic aromatic hydrocarbons by a PMF receptor model. Assessment of potential risk for human health

One year sampling (2011-2012) campaign of airborne PM2.5-bound PAH was performed in Zaragoza, Spain. A source apportionment of total PAH by Positive Matrix Factorization (PMF) was applied in order to quantify potential PAH pollution sources. Four sources were apportioned: coal combustion, vehicular emissions, stationary emissions and unburned/evaporative emissions. Although Directive 2004/107/EC was fulfilled regarding benzo(a)pyrene (BaP), episodes exceeding the limit value of PM2.5 according to Directive 2008/50/EC were found. These episodes of high negative potential for human health were studied, obtaining a different pattern for the exceedances of PM2.5 and the lower assessment threshold of BaP (LATBaP). In both cases, stationary emissions contributed majority to total PAH. Lifetime cancer risk exceeded the unit risk recommended by the World Health Organization for those episodes exceeding the LATBaP and the PM2.5 exceedances for the warm season. For the cold season, the risk was higher for the LATBaP than for the PM2.5 exceedances.

Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts

Wood catalytic pyrolysis using calcium-based materials was studied in an auger reactor at 450°C. Two different catalysts, CaO and CaO·MgO were evaluated and upgraded bio-oils were obtained in both cases. Whilst acidity and oxygen content remarkable decrease, both pH and calorific value increase with respect to the non-catalytic test. Upgrading process was linked to the fact that calcium-based materials could not only fix the CO2-like compounds but also promoted the dehydration reactions. In addition, process simulation demonstrated that the addition of these catalysts, especially CaO, could favour the energetic integration since a lowest circulation of heat carrier between combustor and auger reactor should be needed. An energy self-sustained system was obtained where thermal energy required for biomass drying and for pyrolysis reaction was supplied by non-condensable gas and char combustion, respectively.

Porosity–Acidity Interplay in Hierarchical ZSM‐5 Zeolites for Pyrolysis Oil Valorization to Aromatics

The properties of crude bio-oils attained by the pyrolysis of lignocellulosic biomass can be greatly enhanced by means of catalytic upgrading. Here, we demonstrate an efficient process concept coupling the production of pyrolysis oil from pine wood with a consecutive catalytic upgrading step over hierarchically structured ZSM-5 zeolites to attain aromatic-rich bio-oils. The selective upgrading of these complex mixtures is shown to be tightly connected to the extent of mesopore development and the density of Brønsted acid sites at the mesopore surface. A full product analysis enables elucidation of the impact of mesopore introduction and the acidic properties on the complex reaction network. The preferential occurrence of decarbonylation reactions in hierarchical zeolites versus dehydration transformations in the bulk counterparts is believed to be decisive in promoting increased aromatics formation.

BaP (PAH) air quality modelling exercise over Zaragoza (Spain) using an adapted version of WRF-CMAQ model

Benzo(a)pyrene (BaP) is one of the most dangerous PAH due to its high carcinogenic and mutagenic character. Because of this reason, the Directive 2004/107/CE of the European Union establishes a target value of 1xa0ng/m(3) of BaP in the atmosphere. In this paper, the main aim is to estimate the BaP concentrations in the atmosphere by using last generation of air quality dispersion models with the inclusion of the transport, scavenging and deposition processes for the BaP. The degradation of the particulated BaP by the ozone has been considered. The aerosol-gas partitioning phenomenon in the atmosphere is modelled taking into a count that the concentrations in the gas and the aerosol phases. If the pre-existing organic aerosol concentrations are zero gas/particle equilibrium is established. The model has been validated at local scale with data from a sampling campaign carried out in the area of Zaragoza (Spain) during 12 weeks.

Study of Pb sources by Pb isotope ratios in the airborne PM10 of Zaragoza, Spain

Lead is a toxic trace element which produces harmful effects on human health, even at low concentrations, and it can be useful as ambient pollution tracer because the relative abundance of its four stable isotopes (204, 206, 207 and 208) depends on the emission source. This study was focused on the lead concentrations and isotope ratios in the PM10 of Zaragoza, in order to determine the main Pb pollution sources and to check whether the influence of the prohibition of leaded fuel was worthwhile. Two sampling campaigns from 2001 until 2004, the first one in which leaded gasoline was still effective and the second one with the phase-out, were carried out by using a high-volume air sampler able to trap the particulate matter equal to or less than 10 microm (PM10) on Teflon-coated fibre glass filters. Firstly, the Pb concentrations for the two sampling campaigns were analysed by inductively-coupled plasma optical emission spectrometry (ICP-OES). No statistically significant decrease in the Pb average concentration was obtained from the first to the second sampling. Enrichment factors showed that anthropogenic sources were prevalent during both samplings, in particular during 2001-2002. Afterwards, only those samples with higher concentrations than the limit of quantification of Pb were analysed to determine the lead isotopic composition by inductively-coupled plasma quadrupole mass spectrometry (ICP-QMS). To apply this analytical technique successfully, it was necessary to optimize the parameters affecting the measurement accuracy and precision. Differences were found regarding the lead isotope ratios for both periods finding that anthropogenic sources related to industrial processes were reflected on both campaigns. The gasoline contribution for the first campaign was 23% whereas for the second sampling this contribution was negligible, corroborating the success of the lead policies on the quality of the environment.