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Relatively little is known about the lanthanoid element (La to Lu) chemistry of inhalable urban atmospheric particulate matter (PM). PM samples collected during an air sampling campaign in the Mexico City area contain lanthanoid concentrations of mostly 1-10ng m-3, increasing with mass where resuspension of crustal PM is important (low PM2.5/PM10), but not where fine emissions from traffic and industry dominate (high PM2.5/PM10). Samples show anthropogenic enrichment of lighter over heavier lanthanoids, and Ce enrichment relative to La and Sm occurs in the city center (especially PM10) possibly due to PM from road vehicle catalytic converters. La is especially enriched, although many samples show low La/V values (<0.11), suggesting the dominating influence of fuel oil combustion sources rather than refinery emissions. We use La/Sm v La/Ce, LaCeSm, and LaCeV plots to compare Mexico City aerosols with PM from other cities. Lanthanoid aerosol geochemistry can be used not only to identify refinery pollution events, but also as a marker for different hydrocarbon combustion emissions (e.g., oil or coal power stations) on urban background atmospheric PM. [ABSTRACT FROM AUTHOR]

Time series (1996-2000) of levels of PM (PM10 and TSP) and gaseous pollutants recorded in air quality monitoring networks from Northeastern Spain were interpreted using meteorological data and satellite observations of African dust plumes. The main objective of this study was to identify the processes affecting time variations of PM levels on a day-to-day and seasonal basis. From March to October PM levels at rural, urban, and industrial sites vary as a function of the concatenation of Atlantic air mass advections (Atlantic episodes with Iow PM levels) and regional circulations (regional events with high PM levels, very often associated with high ozone levels), which favor the aging of air masses in the Western Mediterranean basin. During these regional episodes, PM is transported from urban/industrial to rural sites by meso-scale circulations. From November to February Iow PM levels are recorded at rural sites, and variations in PM levels at urban/industrial sites are governed by the successive occurrence of Atlantic episodes and local urban/industrial pollution events. The African dust outbreaks take place throughout the year and may induce PM levels to increase simultaneously in large areas of the Iberian peninsula. The difference between PM concentrations measured at urban and rural sites experiences a seasonal trend similar to that of levels of N0[sub x] and CO, which is characterized by a winter maximum due to the higher frequency of intensive local urban pollution events. However, maximum PM levels are recorded in summer at rural sites owing to the frequent occurrence of regional episodes. Furthermore, in three years of the study period (1997, 1998, and 2000), a secondorder PM maximum was also recorded at rural sites in March owing to intensive African dust outbreaks. [ABSTRACT FROM AUTHOR]

Examines the utilization of zeolites synthesized from coal fly ash in the purification of acid mine waters in Spain. Decontamination tests of acid mine waters; Employment of zeolitic material for heavy metal uptake in water purification processes; Increase of hydrogen concentration through zeolite application.

Focuses on an experiment which involved the use of fly ash by conventional and microwave-assisted hydrothermal alkaline activation, to synthesize zeolitic material. How the zeolite synthesis was studied; Contents of the zeolitic material synthesized from the same fly ash; Results of experiment.

The effect of pH on the dissolution kinetics of NaP1 zeolite, which was produced from the alkaline treatment of coal fly ash and may be used for decontamination of acid mine waters, is studied. The sample contains considerable amounts of accessory phases that partly dissolve during the experiment Therefore, the dissolution rate was estimated during a stage in which the AI/Si ratio was equal to that of NaP1 (0.6). The release rate of these elements is controlled by the dissolution of the zeolite itself during this stage. The dissolution rate of NaP1 slows down with increasing pH in the acidic range, becomes constant at an intermediate pH, and increases with increasing pH in the basic range. The observed changes in rates were described using a rate law based on a surface speciation model. Using this rate law, we calculated the half-life of NaP1 to be about 2 years at near neutral pH and less than 10 days at pH below 3. For the utilization of NaP1 in the treatment of waste waters or acid mine waters, these short half-lives bear two implications: (1) The treated waters must be kept at near neutral pH, and NaP1 should be added periodically to the treated waters in order to compensate for zeolite loss. (2) In water treatment applications that require a relatively short reaction time, the zeolite removed from the effluents should be kept dry in order to avoid its decomposition and the consequent release of the adsorbed metal to the environment. [ABSTRACT FROM AUTHOR]

Coal power plants are producing huge amounts of coal ash that may be applied to a variety of secondary uses. Class F fly ash may act as an excellent scrubber and fixation reagent for highly acidic wastes, which might also contain several toxic trace elements. This paper evaluates the potential of using Class F fly ashes (<20% CaO), in combination with excessive fines from the limestone quarry industry as a fixation reagent. The analysis included leaching experiments (EN12457-2) and several analytical techniques (ICP, SEM, XRD, etc.), which were used in order to investigate the fixation procedure. The fine sludge is used as a partial substitute in concrete that can be used in civil engineering projects, as it an environmentally safe product. [ABSTRACT FROM AUTHOR]

The spatial distribution of PM1 components in the Barcelona metropolitan area was investigated using on-road mobile measurements of atmospheric particle- and gas-phase compounds during the DAURE campaign in March 2009. Positive matrix factorization (PMF) applied to organic aerosol (OA) data yielded 5 factors: hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), and low volatility and semivolatile oxygenated OA (LV-OOA and SV-OOA). The area under investigation (~500 km²) was divided into six zones (city center, harbor, industrial area, precoastal depression, 2 mountain ranges) for measurements and data analysis. Mean zonal OA concentrations are 4.9-9.5 µg m-3. The area is heavily impacted by local primary emissions (HOA 14-38%, COA 10-18%, BBOA 10-12% of OA); concentrations of traffic-related components, especially black carbon, are biased high due to the on-road nature of the measurements. The formation of secondary OA adds more than half of the OA burden outside the city center (SV-OOA 14-40%, LV-OOA 17-42% of OA). A case study of one measurement drive from the shore to the precoastal mountain range furthest downwind of the city center indicates the importance of nonfossil over anthropogenic secondary OA based on OA/CO. [ABSTRACT FROM AUTHOR]

A novel on-board system was tested to characterize size-resolved particle number emission patterns under real-world driving conditions, running in a EURO4 diesel vehicle and in a typical urban circuit in Madrid (Spain). Emission profiles were determined as a function of driving conditions. Source apportionment by Positive Matrix Factorization (PMF) was carried out to interpret the real-world driving conditions. Three emission patterns were identified: (F1) cruise conditions, with medium-high speeds, contributing in this circuit with 60% of total particle number and a particle size distribution dominated by particles >52 nm and around 60 nm; (F2) transient conditions, stop-and-go conditions at medium-high speed, contributing with 25% of the particle number and mainly emitting particles in the nucleation mode; and (F3) creep-idle conditions, representing traffic congestion and frequent idling periods, contributing with 14% to the total particle number and with particles in the nucleation mode (<29.4 nm) and around 98 nm. We suggest potential approaches to reduce particle number emissions depending on particle size and driving conditions. Differences between real-world emission patterns and regulatory cycles (NEDC) are also presented, which evidence that detecting particle number emissions <40 nm is only possible under real-world driving conditions. [ABSTRACT FROM AUTHOR]

An unusual and different speciation of Hg in the outgoing gaseous stream of the flue gas desulfurization (OUT-FGD) system was revealed at two Spanish power plants (PP1 and PP2) equipped with a forced oxidation wet FGD system with water recirculation to the scrubber. At PP1 and PP2, a high proportion of Hg escapes from the electrostatic precipitator in gaseous form, Hg2+ (75-86%) being the species that enters the FGD. At PP1 Hg0 (71%) was the prevalent Hg OUT-FGD species, whereas at PP2 Hg2+ was the prevalent Hg OUT-FGD species in 2007 (66%) and 2008 (87%). The unusual speciation of gaseous Hg OUT-FGD and the different Hg retentions between 2007 and 2008 at PP2 were attributable to the evaporation of HgCl2 particles from the aqueous phase of gypsum slurry in the OUT-FGD gas and the Al additive used at PP2, respectively. The Al additive induced the retention of Hg as HgS in the 2007 FGD gypsum, thus reducing gaseous emissions of Hg in the OUT-FGD gas. [ABSTRACT FROM AUTHOR]

African dust (AD) contributions to particulate matter (PM) levels may be reported by Member States to the European Commission during justification of exceedances of the daily limit value (DLV). However, the detection and subsequent quantification of the AD contribution to PM levels is complex, and only two measurement-based methods are available in the literature: the Spanish-Portuguese reference method (SPR), and the Tel Aviv University method (TAU). In the present study, both methods were assessed. The SPR method was more conservative in the detection of episodes (71 days identified as AD by SPR, vs 81 by TAU), as it is less affected by interferences with local dust sources. The mean annual contribution of AD was lower with the TAU method than with SPR (2.7 vs 3.5 ± 1.5 μg/m³). The SPR and TAU AD time series were correlated with daily aluminum levels (a known tracer of AD), as well as with an AD source identified by the Positive Matrix Factorization (PMF) receptor model. Higher r² values were obtained with the SPR method than with TAU in both cases (r² = 0.72 vs 0.56, y = 0.05x vs y = 0.06x with aluminum levels; r² = 0.79 vs 0.43, y = 0.8x vs y - 0.4x with the PMF source). We conclude that the SPR method is more adequate from an EU policy perspective (justification of DLV exceedances) due to the fact that it is more conservative than the TAU method. Based on our results, the TAU method requires adaptation of the thresholds in the algorithm to refine detection of low-impact episodes and avoid misclassification of local events as AD. [ABSTRACT FROM AUTHOR]

The present investigation, carried out as a case study in a typical major city situated in a European coal combustion region (Krakow, Poland), aims at quantifying the impact on the urban air quality of residential heating by coal combustion in comparison with other potential pollution sources such as power plants, industry, and traffic. Emissions were measured for 20 major sources, including small stoves and boilers, and the particulate matter (PM) was analyzed for 52 individual compounds together with outdoor and indoor PM10 collected during typical winter pollution episodes. The data were analyzed using chemical mass balance modeling (CMB) and constrained positive matrix factorization (CMF) yielding source apportionments for PM10 B(a)P, and other regulated air pollutants namely Cd, Ni, As, and Pb. The results are potentially very useful for planning abatement strategies in all areas of the world, where coal combustion in small appliances is significant. During the studied pollution episodes in Krakow, European air quality limits were exceeded with up to a factor 8 for PM10 and up to a factor 200 for B(a)P. The levels of these air pollutants were accompanied by high concentrations of azaarenes, known markers for inefficient coal combustion. The major culprit for the extreme pollution levels was demonstrated to be residential heating by coal combustion in small stoves and boilers (>50% for PM10 and >90% B(a)P), whereas road transport (<10% for PM10 and <3% for B(a)P), and industry (4-15% for PM10 and <6% for B(a)P) played a lesser role. The indoor PM10 and B(a)P concentrations were at high levels similar to those of outdoor concentrations and were found to have the same sources as outdoors. The inorganic secondary aerosol component of PM10 amounted to around 30%, which for a large part may be attributed to the industrial emission of the precursors SO2 and NOx. [ABSTRACT FROM AUTHOR]

Despite the increase of commercial shipping around the world, data are yet relatively scarce on the contribution of these emissions to ambient air particulates. One of the reasons is the complexity in the detection and estimation of shipping contributions to ambient particulates in harbor and urban environments, given the similarity with tracers of other combustion sources. This study aimed to identify specific tracers of shipping emissions in a Mediterranean city with an important harbor (Melilla, Spain). Results showed that, for 24 h PM10 and PM2.5 samples, valid tracers of commercial shipping emissions were ratios of V/Ni = 4-5 and V/EC < 2, whereas V/EC > 8 excluded the influence of shipping emissions. Other ratios (V/ S, La/Ce, Zn/Ni, Pb/Zn, OC/EC) and tracers (Pb, Zn) were also tested but did not correlate with this source. Due to the changing composition of diesel fuels, tracers in the Mediterranean Sea may not be representative in other regions of the world and vice versa. The contribution of shipping emissions to ambient particulate matter (PM) urban background levels was quantified by positive matrix factorization (PMF), resulting in 2% and 4% of mean annual PM10 levels (0.8 μg/m3 primary particles and 1.7 μg/m3 secondary particles, with 20% uncertainty) and 14% of mean annual PM2.5 levels (2.6 μg/m3). [ABSTRACT FROM AUTHOR]

This work describes the first analytical method specifically developed for the multianalyte determination of several drugs of abuse and their metabolites in air. The methodology is based on pressurized liquid extraction (PLE) of atmospheric particles collected by means of high volume sampler equipped with quartz microfiber filters and subsequent analysis of the extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Up to 17 different com- pounds belonging to five different chemical classes (cocainics, amphetamine-like compounds, opioids, cannabinoids, and lysergic compounds) are determined by means of this methodology. Acquisition is performed in the selected reaction monitoring (SRM) mode recording two transitions per compound (except for amphetamine). Quantitation by the internal standard method is based on the use of surrogated deuterated standards. The method has been validated in terms of linearity, accuracy, repeatability and sensitivity with satisfactory results. Absolute recoveries were above 50% for most investigated compounds. Method precision showed relative standard deviations (RSD) below 13% for all compounds, except for cannabinoids. The method limits of determination ranged from 0.35 pg/m3 (for 2-oxo- 3-hydroxy-LSD) to 22.55 pg/m3 (for 11-nor-9 carboxy THC). Finally, as a part of the method validation, the optimized procedure was applied to the analysis of ambient air samples (fine grain-size parliculates, PM2.5) collected at two urban background sites in Barcelona and Madrid (Spain). Results evidenced the presence of cocaine, benzoilecgonine, tetrahydrocannabinol, ecstasy, amphetamine, methamphetamine, and heroin in some or all of the samples investigated. The highest mean daily levels corresponded to cocaine (850 pg/m3) followed by heroin (143 pg/m3). [ABSTRACT FROM AUTHOR]

Co-firing of coal with inexpensive secondary fuels such as petroleum coke is expected to increase in the near future in the EU given that it may provide certain economic and environmental benefits with respect to coal combustion. However, changes in the feed fuel composition of power plants may modify the bulk content and the speciation of a number of elements in fly ash and slag. Consequently, leachability of these byproducts also can be modified. This study is focused on identifying the changes in the environmental quality of co-fired fly ash and slag induced by a modification of the petcoke/coal ratio. Petcoke was found to increase the leachable content of V and Mo and to enhance the mobility of S and As. However, with the exception of these elements,the addition of this secondary fuel did not drastically modify the bulk composition or the overall leachability of the resulting fly ash and slag. [ABSTRACT FROM AUTHOR]