Spatiotemporal variations of tropospheric ozone in Spain (2008-2019).

This study aims to support the development of Spain's Ozone Mitigation Plan by evaluating the present-day spatial variation (2015-2019) and trends (2008-2019) for seven ground-level ozone (O3) metrics relevant for human/ecosystems exposure and regulatory purposes. Results indicate that the spatial variation of O3 depends on the part of the O3 distribution being analyzed. Metrics associated with moderate O3 concentrations depict an increasing O3 gradient between the northern and Mediterranean coasts due to climatic factors, while for metrics considering the upper end of the O3 distribution, this climatic gradient tends to attenuate in favor of hotspot regions pointing to relevant local/regional O3 formation. A classification of atmospheric regions in Spain is proposed based on their O3 pollution patterns, to identify priority areas (or O3 hotspots) where local/regional precursor abatement might significantly reduce O3 during pollution episodes. The trends assessment reveals a narrowing of the O3 distribution at the national level, with metrics influenced by lower concentrations tending to increase over time, and those reflecting the higher end of the O3 distribution tending to decrease. While most stations show no statistically significant variations, contrasting O3 trends are evident among the O3 hotspots. The Madrid area exhibits the majority of upward trends across all metrics, frequently with the highest increasing rates, implying increasing O3 associated with both chronic and episodic exposure. The Valencian Community area exhibits a mixed variation pattern, with moderate to high O3 metrics increasing and peak metrics decreasing, while O3 in areas downwind of Barcelona, the Guadalquivir Valley and Puertollano shows no variations. Sevilla is the only large Spanish city with generalized O3 decreasing trends. The different O3 trends among hotspots highlight the need for mitigation measures to be designed at a local/regional scale to be effective. This approach may offer valuable insights for other countries developing O3 mitigation plans.

Size-resolved chemical composition and toxicity of particles released from refit operations in shipyards.

Ship refit and repair operations in shipyards generate aerosol emissions with high potential for environmental impacts. Metal-bearing nano-, fine and coarse particles are incidentally formed and can be released to indoor and ambient air and the aquatic environment. This work aimed to further the understanding of these impacts by characterising particle size-resolved chemical composition (15 nm - 10 µm), organophosphate esters (OPEs) content (e.g., plasticisers) and cytotoxic and genotoxic potential. Results showed that nanoparticle emissions (20-110 nm) took place in bursts, coinciding with the use of mechanical abraders and spray-painting guns. Tracers of these activities were Sc, V, Cr, Co, Ni, Cu, Rb, Nb, and Cs. Key components were V and Cu, probably sourcing from nanoadditives in the coatings. Abrasion of coatings also emitted OPEs, especially from old paints. Toxicity assessments consistently evidenced hazardous potential for the different endpoints assessed, for a number of samples. Exposures to spray-painting aerosols were linked with reduced cell viability (cytotoxicity), significant generation of reactive oxygen species (ROS), and increases in micronuclei frequency (genotoxicity). Even though spray-painting did not contribute significantly to aerosol mass or number concentrations, it was a major driver of potential health effects. Results suggest that aerosol chemical composition (e.g., content in nano-sized Cu or V) may have a larger impact on toxicity than aerosol concentration. While direct human exposures may be prevented using personal and collective protective equipment and environmental release can be minimised by enclosures and filtration systems, impacts on ambient air and the aquatic environment cannot be fully prevented. The continued use of good practices (exhaust, dilution, general ventilation systems, PPE, already in place) is encouraged to reduce inhalation exposures inside the tents. Understanding the size-resolved chemical and toxicological properties of aerosols is key to reducing human health and environmental impacts of ship refit operations in shipyards.

Channeled PM10, PM2.5 and PM1 Emission Factors Associated with the Ceramic Process and Abatement Technologies.

A sampling methodology and a mathematical data treatment were developed that enable to determine not only total suspended particulates (TSP) emitted at channeled sources but also the PM10, PM2.5, and PM1 mass fractions (w10, w2.5, and w1) and emission factors (E.F.), using a seven-stage cascade impactor. Moreover, a chemical analysis was performed to identify the elements present in these emissions. The proposed methodology was applied to different stages of the ceramic process, including ambient temperature (milling, shaping, glazing) and medium-high-temperature (spray-drying, drying, firing, and frit melting) stages. In total, more than 100 measurements were performed (pilot scale and industrial scale), which leads to a measurement time of 1500 h. Related to the mass fractions, in general, the mean values of w10 after the fabric filters operated at high performance are high and with little dispersion (75-85%), and it is also observed that they are practically independent of the stage considered, i.e., they are not significantly dependent on the initial PSD of the stream to be treated. In the case of the fine fraction w2.5, the behavior is more complex (w2.5: 30-60%), probably because the only variable is not the cleaning system, but also the nature of the processed material. Regarding abatement measures, the use of high-efficiency cleaning systems considerably reduces the emission factors obtained for fractions PM10, PM2.5, and PM1. In reference to chemical analysis, the presence of ZrO2 and Ni in the spray-drying and pressing stages, the significant concentration of ZrO2 in the glazing stage, the presence of Pb, As, and Zn in the firing stage, and the presence of Zn, Pb, Cd, and As compounds in the frits manufacturing should all be highlighted. Nevertheless, it should be pointed out that the use of some compounds, such as cadmium and lead, has been very limited in the last years and, therefore, presumably, the presence of these elements in the emissions should have been also reduced in the same way.

Unveiling the Toxicity of Fine and Nano-Sized Airborne Particles Generated from Industrial Thermal Spraying Processes in Human Alveolar Epithelial Cells.

High-energy industrial processes have been associated with particle release into workplace air that can adversely affect workers' health. The present study assessed the toxicity of incidental fine (PGFP) and nanoparticles (PGNP) emitted from atmospheric plasma (APS) and high-velocity oxy-fuel (HVOF) thermal spraying. Lactate dehydrogenase (LDH) release, 2-(4-nitrophenyl)-2H-5-tetrazolio]-1,3-benzene disulfonate (WST-1) metabolisation, intracellular reactive oxygen species (ROS) levels, cell cycle changes, histone H2AX phosphorylation (γ-H2AX) and DNA damage were evaluated in human alveolar epithelial cells at 24 h after exposure. Overall, HVOF particles were the most cytotoxic to human alveolar cells, with cell viability half-maximal inhibitory concentration (IC50) values of 20.18 µg/cm2 and 1.79 µg/cm2 for PGFP and PGNP, respectively. Only the highest tested concentration of APS-PGFP caused a slight decrease in cell viability. Particle uptake, cell cycle arrest at S + G2/M and γ-H2AX augmentation were observed after exposure to all tested particles. However, higher levels of γ-H2AX were found in cells exposed to APS-derived particles (~16%), while cells exposed to HVOF particles exhibited increased levels of oxidative damage (~17% tail intensity) and ROS (~184%). Accordingly, APS and HVOF particles seem to exert their genotoxic effects by different mechanisms, highlighting that the health risks of these process-generated particles at industrial settings should not be underestimated.

In Vitro Toxicity of Industrially Relevant Engineered Nanoparticles in Human Alveolar Epithelial Cells: Air-Liquid Interface versus Submerged Cultures.

Diverse industries have already incorporated within their production processes engineered nanoparticles (ENP), increasing the potential risk of worker inhalation exposure. In vitro models have been widely used to investigate ENP toxicity. Air-liquid interface (ALI) cell cultures have been emerging as a valuable alternative to submerged cultures as they are more representative of the inhalation exposure to airborne nano-sized particles. We compared the in vitro toxicity of four ENP used as raw materials in the advanced ceramics sector in human alveolar epithelial-like cells cultured under submerged or ALI conditions. Submerged cultures were exposed to ENP liquid suspensions or to aerosolised ENP at ALI. Toxicity was assessed by determining LDH release, WST-1 metabolisation and DNA damage. Overall, cells were more sensitive to ENP cytotoxic effects when cultured and exposed under ALI. No significant cytotoxicity was observed after 24 h exposure to ENP liquid suspensions, although aerosolised ENP clearly affected cell viability and LDH release. In general, all ENP increased primary DNA damage regardless of the exposure mode, where an increase in DNA strand-breaks was only detected under submerged conditions. Our data show that at relevant occupational concentrations, the selected ENP exert mild toxicity to alveolar epithelial cells and exposure at ALI might be the most suitable choice when assessing ENP toxicity in respiratory models under realistic exposure conditions.

Evaluation of One- and Two-Box Models as Particle Exposure Prediction Tools at Industrial Scale.

One- and two-box models have been pointed out as useful tools for modelling indoor particle exposure. However, model performance still needs further testing if they are to be implemented as trustworthy tools for exposure assessment. The objective of this work is to evaluate the performance, applicability and reproducibility of one- and two-box models on real-world industrial scenarios. A study on filling of seven materials in three filling lines with different levels of energy and mitigation strategies was used. Inhalable and respirable mass concentrations were calculated with one- and two-box models. The continuous drop and rotating drum methods were used for emission rate calculation, and ranges from a one-at-a-time methodology were applied for local exhaust ventilation efficiency and inter-zonal air flows. When using both dustiness methods, large differences were observed for modelled inhalable concentrations but not for respirable, which showed the importance to study the linkage between dustiness and processes. Higher model accuracy (ratio modelled vs. measured concentrations 0.5-5) was obtained for the two- (87%) than the one-box model (53%). Large effects on modelled concentrations were seen when local exhausts ventilation and inter-zonal variations where parametrized in the models. However, a certain degree of variation (10-20%) seems acceptable, as similar conclusions are reached.

Lessons from the COVID-19 air pollution decrease in Spain: Now what?

We offer an overview of the COVID-19 -driven air quality changes across 11 metropolises in Spain with the focus on lessons learned on how continuing abating pollution. Traffic flow decreased by up to 80% during the lockdown and remained relatively low during the full relaxation (June and July). After the lockdown a significant shift from public transport to private vehicles (+21% in Barcelona) persisted due to the pervasive fear that using public transport might increase the risk of SARS-CoV-2 infection, which need to be reverted as soon as possible. NO2 levels fell below 50% of the WHO annual air quality guidelines (WHOAQGs), but those of PM2.5 were reduced less than expected due to the lower contributions from traffic, increased contributions from agricultural and domestic biomass burning, or meteorological conditions favoring high secondary aerosol formation yields. Even during the lockdown, the annual PM2.5 WHOAQG was exceeded in cities within the NE and E regions with high NH3 emissions from farming and agriculture. Decreases in PM10 levels were greater than in PM2.5 due to reduced emissions from road dust, vehicle wear, and construction/demolition. Averaged O3 daily maximum 8-h (8hDM) experienced a generalized decrease in the rural receptor sites in the relaxation (June-July) with -20% reduced mobility. For urban areas O3 8hDM responses were heterogeneous, with increases or decreases depending on the period and location. Thus, after canceling out the effect of meteorology, 5 out of 11 cities experienced O3 decreases during the lockdown, while the remaining 6 either did not experience relevant reductions or increased. During the relaxation period and coinciding with the growing O3 season (June-July), most cities experienced decreases. However, the O3 WHOAQG was still exceeded during the lockdown and full relaxation periods in several cities. For secondary pollutants, such as O3 and PM2.5, further chemical and dispersion modeling along with source apportionment techniques to identify major precursor reduction targets are required to evaluate their abatement potential.

Toxicity assessment of industrial engineered and airborne process-generated nanoparticles in a 3D human airway epithelial in vitro model.

The advanced ceramic technology has been pointed out as a potentially relevant case of occupational exposure to nanoparticles (NP). Not only when nanoscale powders are being used for production, but also in the high-temperature processing of ceramic materials there is also a high potential for NP release into the workplace environment. In vitro toxicity of engineered NP (ENP) [antimony tin oxide (Sb2O3•SnO2; ATO); zirconium oxide (ZrO2)], as well as process-generated NP (PGNP), and fine particles (PGFP), was assessed in MucilAir™ cultures at air-liquid interface (ALI). Cultures were exposed during three consecutive days to varying doses of the aerosolized NP. General cytotoxicity [lactate dehydrogenase (LDH) release, WST-1 metabolization], (oxidative) DNA damage, and the levels of pro-inflammatory mediators (IL-8 and MCP-1) were assessed. Data revealed that ENP (5.56 µg ATO/cm2 and 10.98 µg ZrO2/cm2) only caused mild cytotoxicity at early timepoints (24 h), whereas cells seemed to recover quickly since no significant changes in cytotoxicity were observed at late timepoints (72 h). No meaningful effects of the ENP were observed regarding DNA damage and cytokine levels. PGFP affected cell viability at dose levels as low as ∼9 µg/cm2, which was not seen for PGNP. However, exposure to PGNP (∼4.5 µg/cm2) caused an increase in oxidative DNA damage. These results indicated that PGFP and PGNP exhibit higher toxicity potential than ENP in mass per area unit. However, the presence of a mucociliary apparatus, as it occurs in vivo as a defense mechanism, seems to considerably attenuate the observed toxic effects. Our findings highlight the potential hazard associated with exposure to incidental NP in industrial settings.

Nanoparticle exposure and hazard in the ceramic industry: an overview of potential sources, toxicity and health effects.

The ceramic industry is an industrial sector of great impact in the global economy that has been benefiting from advances in materials and processing technologies. Ceramic manufacturing has a strong potential for airborne particle formation and emission, namely of ultrafine particles (UFP) and nanoparticles (NP), meaning that workers of those industries are at risk of potential exposure to these particles. At present, little is known on the impact of engineered nanoparticles (ENP) on the environment and human health and no established Occupational Exposure Limits (OEL) or specific regulations to airborne nanoparticles (ANP) exposure exist raising concerns about the possible consequences of such exposure. In this paper, we provide an overview of the current knowledge on occupational exposure to NP in the ceramic industry and their impact on human health. Possible sources and exposure scenarios, a summary of the existing methods for evaluation and monitoring of ANP in the workplace environment and proposed Nano Reference Values (NRV) for different classes of NP are presented. Case studies on occupational exposure to ANP generated at different stages of the ceramic manufacturing process are described. Finally, the toxicological potential of intentional and unintentional ANP that have been identified in the ceramic industry workplace environment is discussed based on the existing evidence from in vitro and in vivo inhalation toxicity studies.

Environmental comparison of indoor floor coverings.

Appropriate selection of construction materials plays a major role in a building's sustainable profile. The study sets out a comparative life cycle assessment of indoor flooring systems of different nature. The flooring systems consisted of coverings and, where required, bonding material and/or impact soundproofing material. The following coverings were assessed: inorganic (natural stone and ceramic tiles), polymer (carpeting and PVC), and wood-based (laminate and parquet) coverings. The life cycle assessment scope was defined cradle to cradle, i.e. product stage, transport to the construction site, installation of all construction elements, use, and valorisation by recycling, as end-of-life transition scenario towards a circular economy. In the use stage, three scenarios were defined as a function of pedestrian traffic intensity, which determined maintenance, repair, and replacement operations and frequencies. The environmental impacts of the coverings product stage were taken from previously assessed and selected Environmental Product Declarations (EPDs), as these are standardised public documents devised to provide environmental life cycle information. The method adopted in the study suggests that, though the use of EPDs as information source is interesting, erroneous conclusions may be drawn if the EPDs are not comparable and/or if the comparison is not made in the building context. The results indicate that the flooring systems with inorganic coverings performed best in the global warming, acidification, eutrophication, photochemical ozone creation, and abiotic depletion for fossil resources impact categories, whereas laminates performed best in the abiotic depletion for non-fossil resources and ozone layer depletion impact categories. The carpet flooring system performed worst in every impact category except photochemical ozone creation potential.

Modeling of High Nanoparticle Exposure in an Indoor Industrial Scenario with a One-Box Model.

Mass balance models have proved to be effective tools for exposure prediction in occupational settings. However, they are still not extensively tested in real-world scenarios, or for particle number concentrations. An industrial scenario characterized by high emissions of unintentionally-generated nanoparticles (NP) was selected to assess the performance of a one-box model. Worker exposure to NPs due to thermal spraying was monitored, and two methods were used to calculate emission rates: the convolution theorem, and the cyclic steady state equation. Monitored concentrations ranged between 4.2 × 104-2.5 × 105 cm-3. Estimated emission rates were comparable with both methods: 1.4 × 1011-1.2 × 1013 min-1 (convolution) and 1.3 × 1012-1.4 × 1013 min-1 (cyclic steady state). Modeled concentrations were 1.4-6 × 104 cm-3 (convolution) and 1.7-7.1 × 104 cm-3 (cyclic steady state). Results indicated a clear underestimation of measured particle concentrations, with ratios modeled/measured between 0.2-0.7. While both model parametrizations provided similar results on average, using convolution emission rates improved performance on a case-by-case basis. Thus, using cyclic steady state emission rates would be advisable for preliminary risk assessment, while for more precise results, the convolution theorem would be a better option. Results show that one-box models may be useful tools for preliminary risk assessment in occupational settings when room air is well mixed.

Testing the performance of one and two box models as tools for risk assessment of particle exposure during packing of inorganic fertilizer.

Modelling of particle exposure is a useful tool for preliminary exposure assessment in workplaces with low and high exposure concentrations. However, actual exposure measurements are needed to assess models reliability. Worker exposure was monitored during packing of an inorganic granulate fertilizer at industrial scale using small and big bags. Particle concentrations were modelled with one and two box models, where the emission source was estimated with the fertilizer's dustiness index. The exposure levels were used to calculate inhaled dose rates and test accuracy of the exposure modellings. The particle number concentrations were measured from worker area by using a mobility and optical particle sizer which were used to calculate surface area and mass concentrations. The concentrations in the worker area during pre-activity ranged 63,797-81,073 cm-3, 4.6 × 106 to 7.5 × 106 µm2 cm-3, and 354 to 634 µg m-3 (respirable mass fraction) and during packing 50,300 to 85,949 cm-3, 4.3 × 106 to 7.6 × 106 µm2 cm-3, and 279 to 668 µg m-3 (respirable mass fraction). Thus, the packing process did not significantly increase the exposure levels. Chemical exposure was also under control based on REACH standards. The particle surface area deposition rate in respiratory tract was up to 7.6 × 106 µm2 min-1 during packing, with 52%-61% of deposition occurring in the alveolar region. Ratios of the modelled and measured concentrations were 0.98 ±â€¯0.19 and 0.84 ±â€¯0.12 for small and big bags, respectively, when using the one box model, and 0.88 ±â€¯0.25 and 0.82 ±â€¯0.12, when using the two box model. The modelling precision improved for both models when outdoor particle concentrations were included. This study shows that exposure concentrations in a low emission industrial scenario, e.g. during packing of a fertilizer, can be predicted with a reasonable accuracy by using the concept of dustiness and mass balance models.

On the Relationship between Exposure to Particles and Dustiness during Handling of Powders in Industrial Settings.

Exposure to ceramic powders, which is frequent during handling operations, is known to cause adverse health effects. Finding proxy parameters to quantify exposure is useful for efficient and timely exposure assessments. Worker exposure during handling of five materials [a silica sand (SI1), three quartzes (Q1, Q2, and Q3), and a kaolin (K1)] with different particle shape (prismatic and platy) and sizes (3.4-120 µm) was assessed. Materials handling was simulated using a dry pendular mill under two different energy settings (low and high). Three repetitions of two kilos of material were carried out per material and energy conditions with a flow rate of 8-11 kg h-1. The performance of the dustiness index as a predictor of worker exposure was evaluated correlating material's dustiness indexes (with rotating drum and continuous drop) with exposure concentrations. Significant impacts on worker exposure in terms of inhalable and respirable mass fractions were detected for all materials. Mean inhalable mass concentrations during background were always lower than 40 µg m-3 whereas during material handling under high energy settings mean concentrations were 187, 373, 243, 156, and 430 µg m-3 for SI1, Q1, Q2, Q3, and K1, respectively. Impacts were not significant with regard to particle number concentration: background particle number concentrations ranged between 10 620 and 46 421 cm-3 while during handling under high energy settings they were 20 880 - 40 498 cm-3. Mean lung deposited surface area during background ranged between 27 and 101 µm2 cm-3 whereas it ranged between 22 and 42 µm2 cm-3 during materials handling. TEM images evidenced the presence of nanoparticles (≤100 nm) in the form of aggregates (300 nm-1 µm) in the worker area, and a slight reduction on mean particle size during handling was detected. Dustiness and exposure concentrations showed a high degree of correlation (R2 = 0.77-0.97) for the materials and operating conditions assessed, suggesting that dustiness could be considered a relevant predictor for workplace exposure. Nevertheless, the relationship between dustiness and exposure is complex and should be assessed for each process, taking into account not only material behaviour but also energy settings and workplace characteristics.

Workplace Exposure to Nanoparticles during Thermal Spraying of Ceramic Coatings.

Thermal spraying is widely used for industrial-scale application of ceramic coatings onto metallic surfaces. The particular process has implications for occupational health, as the high energy process generates high emissions of metal-bearing nanoparticles. Emissions and their impact on exposure were characterized during thermal spraying in a work environment, by monitoring size-resolved number and mass concentrations, lung-deposited surface area, particle morphology, and chemical composition. Along with exposure quantification, the modal analysis of the emissions assisted in distinguishing particles from different sources, while an inhalation model provided evidence regarding the potential deposition of particulate matter on human respiratory system. High particle number (>10(6) cm-3; 30-40 nm) and mass (60-600 µgPM1 m-3) concentrations were recorded inside the spraying booths, which impacted exposure in the worker area (10(4)-10(5) cm-3, 40-65 nm; 44-87 µgPM1 m-3). Irregularly-shaped, metal-containing particles (Ni, Cr, W) were sampled from the worker area, as single particles and aggregates (5-200 nm). Energy dispersive X-ray analysis confirmed the presence of particles originated from the coating material, establishing a direct link between the spraying activity and exposure. In particle number count, 90% of the particles were between 26-90 nm. Inhaled dose rates, calculated from the exposure levels, resulted in particle number rates (n˙) between 353 × 10(6)-1024 × 10(6) min-1, with 70% of deposition occurring in the alveolar region. The effectiveness of personal protective equipment (FPP3 masks) was tested under real working conditions. The proper sealing of the spraying booths was identified as a key element for exposure reduction. This study provides high time-resolved aerosol data which may be valuable for validating indoor aerosol models applied to risk assessment.

Organosilane-Based Coating of Quartz Species from the Traditional Ceramics Industry: Evidence of Hazard Reduction Using In Vitro and In Vivo Tests.

The exposure to respirable crystalline silica (RCS), e.g. quartz, in industrial settings can induce silicosis and may cause tumours in chronic periods. Consequently, RCS in the form of quartz and cristobalite has been classified as human lung carcinogen category 1 by the International Agency for Research on Cancer in 1997, acknowledging differences in hazardous potential depending on source as well as chemical, thermal, and mechanical history. The physico-chemical determinants of quartz toxicity are well understood and are linked to density and abundance of surface silanol groups/radicals. Hence, poly-2-vinylpyridine-N-oxide and aluminium lactate, which effectively block highly reactive silanol groups at the quartz surface, have formerly been introduced as therapeutic approaches in the occupational field. In the traditional ceramics industry, quartz-containing raw materials are indispensable for the manufacturing process, and workers are potentially at risk of developing quartz-related lung diseases. Therefore, in the present study, two organosilanes, i.e. Dynasylan® PTMO and Dynasylan® SIVO 160, were tested as preventive, covalent quartz-coating agents to render ceramics production safer without loss in product quality. Coating effectiveness and coating stability (up to 1 week) in artificial alveolar and lysosomal fluids were first analysed in vitro, using the industrially relevant quartz Q1 as RCS model, quartz DQ12 as a positive control, primary rat alveolar macrophages as cellular model system (75 µg cm-2; 4 h of incubation ± aluminium lactate to verify quartz-related effects), and lactate dehydrogenase release and DNA strand break induction (alkaline comet assay) as biological endpoints. In vitro results with coated quartz were confirmed in a 90-day intratracheal instillation study in rats with inflammatory parameters as most relevant readouts. The results of the present study indicate that in particular Dynasylan® SIVO 160 (0.2% w/w of quartz) was able to effectively and stably block toxicity of biologically active quartz species without interfering with technical process quality of certain ceramic products. In conclusion, covalent organosilane coatings of quartz might represent a promising strategy to increase workers' safety in the traditional ceramics industry.

Evaluation of the Dustiness of Different Kaolin Samples.

Several samples of kaolin with different mean particle size were prepared and tested using the continuous drop method, one of the reference test methods according to standard EN 15051:2006 "Workplace atmospheres - Measurement of the dustiness of bulk materials - Requirements and reference test methods." On the other hand, with a view to relating the dustiness of the materials to their properties, particle size distribution, specific surface area, and Hausner ratio of these samples were determined. This article presents a characterization of these samples and an assessment of the influence of some material parameters on dustiness. The results show that dustiness may significantly be affected by mean particle size, specific surface area, and Hausner ratio. Moreover, it is highlighted that a detailed study of the influence of fine particles content on the dustiness was carried out. This information is deemed essential for establishing the most efficient preventive and/or corrective measures to reduce the generation of fugitive emissions of particulate matter during kaolin processing, both into the outside atmosphere (air pollution) and inside the facilities (occupational health).

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.

Application of optimally scaled target factor analysis for assessing source contribution of ambient PM10.

Speciated coarse particulate matter (PM10) data obtained at three air quality monitoring sites in a highly industrialized area in Spain between 2002 and 2007 were analyzed for assessing source contribution of ambient particulate matter (PM). The source apportionment of PM in this area is an especially difficult task. There are industrial mineral dust emissions that need to be separately quantified from the natural sources of mineral PM. On the other hand, the diversity of industrial processes in the area results in a puzzling industrial emissions scenario. To solve this complex problem, a two-step methodology based on the possibilities of the Multilinear Engine was used. Application of positive matrix factorization to the dataset allowed the identification of nine factors relevant to the study area. This preliminary analysis permitted resolving two mineral factors. As a second step, a target rotation was implemented for transforming the mineral factors into experimentally characterized soil resuspension and industrial clay sources. In addition to improving the physical interpretation of these factors, the target rotation reduced the errors arising from the rotational freedom of the solution and the multicollinearity among sources. In this way, the main primary industrial emissions of PM in the zone were identified by this target factor analysis. A marked decrease was observed between 2002 and 2007 for the contributions of industrial sources coinciding with the implementation of mitigation measures in their processes. This study supports the utility of source apportionment methodologies for quantitatively evaluating the effectiveness of the abatement programs for air quality improvement.

Effect of ceramic industrial particulate emission control on key components of ambient PM10.

The relationship between specific particulate emission control and ambient levels of some PM(10) components (Zn, As, Pb, Cs, Tl) was evaluated. To this end, the industrial area of Castellón (Eastern Spain) was selected, where around 40% of the EU glazed ceramic tiles and a high proportion of EU ceramic frits are produced. The PM(10) emissions from the ceramic processes were calculated over the period 2000-2006, taking into account the degree of implementation of corrective measures throughout the study period. Abatement systems were implemented in the majority of the fusion kilns for frit manufacture in the area as a result of the application of the Directive 1996/61/EC, leading to a marked decrease in PM(10) emissions. By contrast, emissions from tile manufacture remained relatively constant because of the few changes in the implementation of corrective measures. On the other hand, ambient PM(10) levels and composition measurements were carried out from 2002 to 2006. A high correlation between PM(10) emissions from frit manufacture and ambient levels of Zn, As, Pb and Cs (R(2) from 0.61 to 0.98) was observed. On the basis of these results, the potential impact of the implementation of corrective measures to reduce emissions from tile manufacture was quantified, resulting in a possible decrease of 3-5 microg/m(3) and 2 microg/m(3) in ambient mineral PM(10) (on an annual basis) in urban and suburban areas, respectively. This relatively simple methodology allows us to estimate the direct effect of a reduction in primary particulate emissions on ambient levels of key particulate components, and to make a preliminary quantification of the possibilities of air quality improvement by means of further emission reduction. Therefore, it is a useful tool for developing future air quality plans in the study area and in other industrialised areas.