PM10 speciation and determination of air quality target levels. A case study in a highly industrialized area of Spain

The paper shows how PM speciation studies allow the evaluation of the strategies to be followed to diminish PM pollution in highly industrialized areas with a large number of potential pollution sources. Evolution of levels and speciation of PM10 in the ceramic producing area of Castelló (East Spain) was studied from April 2002 until December 2005. PM10 levels were measured at one rural (Borriana-rural), two suburban (Almassora and Onda) and three urban (Borriana-urban, L'Alcora and Vila-real) sites, all influenced by the ceramics industry. Average PM10 levels varied between 27 and 36 microg/m3 for the study period. Evaluation of 1996-2005 PM data from Onda shows a clear decrease of PM levels since the beginning of 2002. Summer peak levels and winter minima occurred at both rural and suburban sites, whereas urban sites had no clear seasonal trend, with high PM10 episodes being due variously to local, regional, and African dust intrusion events. PM10 chemical analysis at four of the sites showed the dominant constituent to be mineral matter, exceeding by 5-12 microg/m3 the usual ranges of annual mineral loadings in PM10 at comparable Spanish urban or regional background sites with no industrial influence. Given current PM10 loadings, we recommend a lowering target of 3-5 microg/m3 of the annual mean at the urban sites, which should be achievable given available emission abatement techniques.     

Variations in vanadium, nickel and lanthanoid element concentrations in urban air

The emission of trace metal pollutants by industry and transport takes place on a scale large enough to alter atmospheric chemistry and results in measurable differences between the urban background of inhalable particulate matter (PM) in different towns. This is particularly well demonstrated by the technogenic release into the atmosphere of V, Ni, and lanthanoid elements. We compare PM concentrations of these metals in large datasets from five industrial towns in Spain variously influenced by emissions from refinery, power station, shipping, stainless steel, ceramic tiles and brick-making. Increased La/Ce values in urban background inhalable PM, due to La-contamination from refineries and their residual products (fuel oils and petcoke), contrast with Ce-rich emissions from the ceramic related industry, and clearly demonstrate the value of this ratio as a sensitive and reliable tracer for many point source emissions. Similarly, anomalously high V/Ni values (> 4) can detect the influence of nearby high-V petcoke and fuel oil combustion, although the use of this ratio in urban background PM is limited by overlapping values in natural and anthropogenic materials. Geochemical characterisation of urban background PM is a valuable compliment to the physical monitoring of aerosols widely employed in urban areas, especially given the relevance of trace metal inhalation to urban health issues.     

Enantiomer separation by countercurrent chromatography using cinchona alkaloid derivatives as chiral selectors

Cinchona-derived anion-exchange-type chiral selectors have been adapted and employed in countercurrent chromatography (CCC) for the separation of enantiomers of N-derivatized amino acids and 2-aryloxypropionic acids. The accurate optimization of the enantioseparation in terms of solvent system composition, pH values, ionic strength, and CCC operating conditions was performed. A wide range of solvent mixtures was evaluated. Successful resolutions were achieved in systems such as ammonium acetate buffer/tert-amyl alcohol/methanol/heptane and especially ammonium acetate buffer/methyl isobutyl ketone or diisopropyl ether. Up to 300 mg (0.92 mmol) of N-(3,5-dinitrobenzoyl)-(+/-)-leucine was totally resolved in a single run using a 10 mM concentration of chiral selector in 122 mL of stationary phase. This amount could be increased up to 900 mg (2.77 mmol) when pH-zone-refining mode was applied. The results here presented account for the high potential of CCC as a preparative enantiomer separation technique.     

Bioaerosols in the Barcelona subway system

Subway systems worldwide transport more than 100 million people daily; therefore, air quality on station platforms and inside trains is an important urban air pollution issue. We examined the microbiological composition and abundance in space and time of bioaerosols collected in the Barcelona subway system during a cold period. Quantitative PCR was used to quantify total bacteria, Aspergillus fumigatus, influenza A and B, and rhinoviruses. Multitag 454 pyrosequencing of the 16S rRNA gene was used to assess bacterial community composition and biodiversity. The results showed low bioaerosol concentrations regarding the targeted microorganisms, although the bacterial bioburden was rather high (10⁴ bacteria/m³). Airborne bacterial communities presented a high degree of overlap among the different subway environments sampled (inside trains, platforms, and lobbies) and were dominated by a few widespread taxa, with Methylobacterium being the most abundant genus. Human‐related microbiota in sequence dataset and ascribed to potentially pathogenic bacteria were found in low proportion (maximum values below 2% of sequence readings) and evenly detected. Hence, no important biological exposure marker was detected in any of the sampled environments. Overall, we found that commuters are not the main source of bioaerosols in the Barcelona subway system.     

Preparative enantiomer separation of dichlorprop with a cinchona-derived chiral selector employing centrifugal partition chromatography and high-performance liquid chromatography: a comparative study

A countercurrent chromatography protocol for support-free preparative enantiomer separation of the herbicidal agent 2-(2,4-dichlorphenoxy)propionic acid (dichlorprop) was developed utilizing a purposefully designed, highly enantioselective chiral stationary-phase additive (CSPA) derived from bis-1,4-(dihydroquinidinyl)phthalazine. Guided by liquid-liquid extraction experiments, a solvent system consisting of 10 mM CSPA in methyl tert-butyl ether and 100 mM sodium phosphate buffer (pH 8.0) was identified as a suitable stationary/mobile-phase combination. This solvent system provided an ideal compromise among stationary-phase retention, enantioselectivity, and well-balanced analyte distribution behavior. Using a commercial centrifugal partition chromatography instrument, complete enantiomer separations of up to 366 mg of racemic dichlorprop could be achieved, corresponding to a sample load being equivalent to the molar amount of CSPA employed. Comparison of the preparative performance characteristics of the CPC protocol with that of a HPLC separation using a silica-supported bis-1,4-(dihydroquinidinyl)phthalazine chiral stationary phase CSP revealed comparable loading capacities for both techniques but a significantly lower solvent consumption for CPC. With respect to productivity, HPLC was found to be superior, mainly due to inherent flow rate restrictions of the CPC instrument. Given that further progress in instrumental design and engineering of dedicated, highly enantioselective CSPAs can be achieved, CPC may offer a viable alternative to CSP-based HPLC for preparative-scale enantiomer separation.     

Lanthanoid geochemistry of urban atmospheric particulate matter

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 1-10 ng 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.     

Impact of fugitive emissions in ambient PM levels and composition: A case study in Southeast Spain

The results of this study show the high impact that anthropogenic fugitive emissions of mineral dust have on air quality (levels of PM₁₀, PM_2.5 and some metals) in a region in SE Spain named L'Alacantí. This could be extensive to other areas of Europe with similar characteristics. Fugitive emissions, such as those arising from large public construction works, cement and ceramic manufacturing, mining, heavy industries, handling and transport of powdered raw materials and road dust, are very often left out of emission monitoring and inspections in Europe. The comparative study of daily PM₁₀ series in the area shows how the increase of annual average PM₁₀ concentrations over 40 μg/m³ is due to extreme episodes occurring in 2006 and 2007, at a regional scale, given the simultaneous recording of PM episodes at distant monitoring sites. The annual average values of the PM₁₀ concentrations were close to or slightly higher than 40 μg/m³ (limit value of Directive 2008/50/CE) during 2006–2007 (Alicante-University 39–41, Agost 40–42, Sant Vicent 42–46, Alicante-El Plà 40–42 μg/m³). The main PM₁₀ sources in the zone were identified with the assistance of the PMF receptor model. Six common factors were determined, mineral as a main source (37% at Agost and 32% at Sant Vicent), road traffic, secondary sulfate, petroleum coke, sea spray and industry. Mineralogical studies, with XRD and SEM-EDX techniques, support the hypothesis that the highest PM episodes are associated to fugitive emissions of mineral matter. Despite the fact that L'Alacantí region is a heavily industrialized area with two cement plants and a significant number of ceramic manufacturing plants, the fugitive emissions may have accounted for the exceedances of the PM limit values during these two years, part of them caused by the construction of a highway. These results may contribute to the interpretation of prior studies on source apportionment carried out in Southern Europe, with very high loads of anthropogenic dust in PM₁₀ and PM_2.5.     

Inter- and Intra-Community Variability in Continuous Coarse Particulate Matter (PM10-2.5) Concentrations in the Los Angeles Area

Continuous coarse particulate matter (CPM, PM _10?2.5 ) concentrations were measured hourly at three different sites in the Los Angeles area from April 2008 through May 2009 as part of a larger study of the characteristics and toxicology of CPM. Mean hourly concentrations calculated seasonally ranged from less than 5 μg m ^–3 to near 70 μg m ^–3 at the three sites depending upon the CPM source variability and prevailing meteorology. Different diurnal concentration profiles were observed at each site. Correlation analysis indicates that CPM concentrations can generally be explained by wind-induced road dust re-suspension, particularly in drier seasons. CPM concentrations between the sites were not appreciably correlated and metrics used to assess variability between the sites—the coefficients of divergence—indicated that CPM concentrations were heterogeneous. The relative CPM contribution to observed PM ₁₀ concentrations varied by season and between sites. Additional concurrent CPM data available within a few km of the three sites indicate that intra-community variability can be on the same order as that observed for inter-community variability, although a similar analysis using PM ₁₀ data yielded reduced heterogeneity. The results indicate that accurate exposure assessment to CPM in the Los Angeles area requires measurements of CPM concentrations at different sites with higher temporal resolution than a single daily mean value.