M. Viana

Comparative PM10-PM2.5 source contribution study at rural, urban and industrial sites during PM episodes in Eastern Spain

In this study a set of 340 PM10 and PM2.5 samples collected throughout 16 months at rural, an urban kerbside and an industrial background site (affected by the emissions from the ceramic manufacture and other activities) were interpreted. On the regional scale, the main PM10 sources were mineral dust (mainly Al2O3, Fe, Ti, Sr, CaCO3, Mg, Mn and K), emissions derived from power generation (SO4=, V, Zn and Ni), vehicle exhausts (organic and elemental carbon, NO3- and trace elements) and marine aerosol (Na, Cl and Mg). The latter was not identified in PM2.5. At the industrial site, additional PM10 sources were identified (tile covering in the ceramic production, petrochemical emissions and bio-mass burning from a large orange tree cultivation area). The contribution of each PM source to PM10 and PM2.5 levels experiences significant variations depending on the type of PM episode (Local-urban mainly in autumn-winter, regional mainly in summer, African or Atlantic episode), which are discussed in this study. The results show that it would be very difficult to meet the EU limit values for PM10 established for 2010. The annual mean PM levels are 22.0 microg PM10/m3 at the rural and 49.5 microg PM10/m3 and 33.9 microg PM2.5/m3 at the urban site. The natural contribution in this region, estimated at 6 microg/m3 of natural mineral dust (resulting from the African events and natural resuspension) and 2 microg/m3 of marine aerosol, accounts for 40% of the 2010 EU annual limit value (20 microg PM10/m3). Mineral dust concentrations at the urban and industrial sites are higher than those at the rural site because of the urban road dust and the ceramic-production contributions, respectively. At the urban site, the vehicle exhaust contribution (17 microg/m3) alone is very close to the 2010 EU PM10 limit value. At the rural site, the African dust is the main contributor to PM10 levels during the highest daily mean PM10 events (100th-97th percentile range). At the urban site, the vehicle exhaust product is the main contributor to PM10 and PM2.5 levels during the highest daily mean PM events (100th-85th percentile range). Mineral dust concentrations during African dust events accounts for 20-30 microg/m3 in PM10 and 10-15 microg/m3 in PM2.5. During non-African dust events, mineral dust derived from anthropogenic activities (e.g. urban road dust) is also a significant contributor to PM10, but not to PM2.5.

Process-generated nanoparticles from ceramic tile sintering: Emissions, exposure and environmental release

The ceramic industry is an industrial sector in need of significant process changes, which may benefit from innovative technologies such as laser sintering of ceramic tiles. Such innovations result in a considerable research gap within exposure assessment studies for process-generated ultrafine and nanoparticles. This study addresses this issue aiming to characterise particle formation, release mechanisms and their impact on personal exposure during a tile sintering activity in an industrial-scale pilot plant, as a follow-up of a previous study in a laboratory-scale plant. In addition, possible particle transformations in the exhaust system, the potential for particle release to the outdoor environment, and the effectiveness of the filtration system were also assessed. For this purpose, a tiered measurement strategy was conducted. The main findings evidence that nanoparticle emission patterns were strongly linked to temperature and tile chemical composition, and mainly independent of the laser treatment. Also, new particle formation (from gaseous precursors) events were detected, with nanoparticles <30nm in diameter being formed during the thermal treatment. In addition, ultrafine and nano-sized airborne particles were generated and emitted into workplace air during sintering process on a statistically significant level. These results evidence the risk of occupational exposure to ultrafine and nanoparticles during tile sintering activity since workers would be exposed to concentrations above the nano reference value (NRV; 4×10(4)cm(-3)), with 8-hour time weighted average concentrations in the range of 1.4×10(5)cm(-3) and 5.3×10(5)cm(-3). A potential risk for nanoparticle and ultrafine particle release to the environment was also identified, despite the fact that the efficiency of the filtration system was successfully tested and evidenced a >87% efficiency in particle number concentrations removal.

Industrial sources of primary and secondary organic aerosols in two urban environments in Spain

In urban areas, primary and secondary organic aerosols are typically considered to originate from vehicular traffic emissions. However, industrial emissions within or in the vicinity of urban areas may also be significant contributors to carbonaceous aerosol concentrations. This hypothesis was tested and validated in two urban areas in Spain. The observed unusual dominance of organic carbon (OC) over elemental carbon (EC), the analysis of the variability of OC, EC and OC/EC and their correlation with transport patterns suggested the presence of OC sources associated with industrial activities. A methodology based on chemical speciation of particulate matter (PM) followed by the application of receptor modelling techniques allowed for the identification of the specific industrial sources of OC, which were linked to primary OC emissions from a grain drying plant (cereal) and to secondary OC formation from paper production activities (paper mills), as well as from urban sources and biogenic emissions. This work presents an integrated approach to identifying and characterizing of industrial sources of carbonaceous aerosols in urban areas, aiming to improve the scarce body of literature currently available on this topic.

Intercomparison of a portable and two stationary mobility particle sizers for nanoscale aerosol measurements

ABSTRACT During occupational exposure studies, the use of conventional scanning mobility particle sizers (SMPS) provides high quality data but may convey transport and application limitations. New instruments aiming to overcome these limitations are being currently developed. The purpose of the present study was to compare the performance of the novel portable NanoScan SMPS TSI 3910 with that of two stationary SMPS instruments and one ultrafine condensation particle counter (UCPC) in a controlled atmosphere and for different particle types and concentrations. The results show that NanoScan tends to overestimate particle number concentrations with regard to the UCPC, particularly for agglomerated particles (ZnO, spark generated soot and diesel soot particles) with relative differences >20%. The best agreements between the internal reference values and measured number concentrations were obtained when measuring compact and spherical particles (NaCl and DEHS particles). With regard to particle diameter (modal size), results from NanoScan were comparable < [± 20%] to those measured by SMPSs for most of the aerosols measured. The findings of this study show that mobility particle sizers using unipolar and bipolar charging may be affected differently by particle size, morphologies, particle composition and concentration. While the sizing accuracy of the NanoScan SMPS was mostly within ±25%, it may miscount total particle number concentration by more than 50% (especially for agglomerated particles), thus making it unsuitable for occupational exposure assessments where high degree of accuracy is required (e.g., in tier 3). However, can be a useful instrument to obtain an estimate of the aerosol size distribution in indoor and workplace air, e.g., in tier 2.

Particle-phase concentrations and sources of legacy and novel flame retardants in outdoor and indoor environments across Spain

Levels of particle-phase legacy polybrominated diphenyl ethers (PBDEs), and novel brominated and chlorinated flame retardants, such as decabromodiphenyl ethane (DBDPE) and Dechlorane Plus (DP), were measured in ambient outdoor air, indoor workplace air and indoor dust, in different locations across Spain. PBDE concentrations were generally higher in outdoor ambient air samples than in indoor air, ranging between 1.18 and 28.6 pg m-3, while DP was the main flame retardant (FR) in indoor air (2.90-42.6 pg m-3). A different behavior of legacy versus novel FRs was observed in all the environments and matrices considered, which seemed to indicate a progressive replacement of the former. Although the emission sources could not be fully identified, certain evidences suggested that high outdoor PBDE concentrations could be associated with old goods in landfills and recycling centers, while high indoor DP concentrations were linked to the presence of new electronic devices. A direct impact of land use on outdoor atmospheric DP concentrations was observed, with DP concentrations correlating with high density of buildings within a city. In addition, DP concentrations outdoors correlated with inorganic species with FR properties (e.g., Cr, Cu). Significant differences in the fraction of anti-DP to the total DP (Fanti ratio) were observed between indoor air (PM2.5) and dust (PM10), which could be related with: a) a dependence on particle size, suggesting a higher relative abundance of the anti-isomer in PM10 than in PM2.5, while similar concentrations were recorded for the syn-isomer; b) a higher deposition rate of the anti-isomer compared to the syn-isomer; and/or c) a more accentuated preferential degradation of the anti-isomer linked to artificial light or other agents coexisting in the air. The detectable presence of all the FR families analyzed in indoor air and dust points to the importance of monitoring these compounds in order to minimize human exposure.

Workplace Exposure to Process-Generated Ultrafine and Nanoparticles in Ceramic Processes Using Laser Technology

The ceramic industry is an industrial sector, which has been growing and including innovative technologies such as laser processes. However, there is a considerable research gap within exposure assessment studies for process-generated ultrafine and nanoparticles, especially as a result of such innovations in the manufacturing processes.