Aerosol source apportionment uncertainty linked to the choice of input chemical components.

For a Positive Matrix Factorization (PMF) aerosol source apportionment (SA) studies there is no standard procedure to select the most appropriate chemical components to be included in the input dataset for a given site typology, nor specific recommendations in this direction. However, these choices are crucial for the final SA outputs not only in terms of number of sources identified but also, and consequently, in the source contributions estimates. In fact, PMF tends to reproduce most of PM mass measured independently and introduced as a total variable in the input data, regardless of the percentage of PM mass which has been chemically characterized, so that the lack of some specific source tracers (e.g. levoglucosan) can potentially affect the results of the whole source apportionment study. The present study elaborates further on the same concept, evaluating quantitatively the impact of lacking specific sources' tracers on the whole source apportionment, both in terms of identified sources and source contributions. This work aims to provide first recommendations on the most suitable and critical components to be included in PMF analyses in order to reduce PMF output uncertainty as much as possible, and better represent the most commons PM sources observed in many sites in Western countries. To this aim, we performed three sensitivity analyses on three different datasets across EU, including extended sets of organic tracers, in order to cover different types of urban conditions (Mediterranean, Continental, and Alpine), source types, and PM fractions. Our findings reveal that the vehicle exhaust source resulted to be less sensitive to the choice of analytes, although source contributions estimates can deviate significantly up to 44 %. On the other hand, for the detection of the non-exhaust one is clearly necessary to analyze specific inorganic elements. The choice of not analysing non-polar organics likely causes the loss of separation of exhaust and non-exhaust factors, thus obtaining a unique road traffic source, which provokes a significant bias of total contribution. Levoglucosan was, in most cases, crucial to identify biomass burning contributions in Milan and in Barcelona, in spite of the presence of PAHs in Barcelona, while for the case of Grenoble, even discarding levoglucosan, the presence of PAHs allowed identifying the BB factor. Modifying the rest of analytes provoke a systematic underestimation of biomass burning source contributions. SIA factors resulted to be generally overestimated with respect to the base case analysis, also in the case that ions were not included in the PMF analysis. Trace elements were crucial to identify shipping emissions (V and Ni) and industrial sources (Pb, Ni, Br, Zn, Mn, Cd and As). When changing the rest of input variables, the uncertainty was narrow for shipping but large for industrial processes. Major and trace elements were also crucial to identify the mineral/soil factor at all cities. Biogenic SOA and Anthropogenic SOA factors were sensitive to the presence of their molecular tracers, since the availability of OC alone is unable to separate a SOA factor. Arabitol and sorbitol were crucial to detecting fungal spores while odd number of higher alkanes (C27 to C31) for plant debris.

Discovering oxidative potential (OP) drivers of atmospheric PM10, PM2.5, and PM1 simultaneously in North-Eastern Spain.

Ambient particulate matter (PM) is a major contributor to air pollution, leading to adverse health effects on the human population. It has been suggested that the oxidative potential (OP, as a tracer of oxidative stress) of PM is a possible determinant of its health impact. In this study, samples of PM10, PM2.5, and PM1 were collected roughly every four days from January 2018 until March 2019 at a Barcelona urban background site and Montseny rural background site in northeastern Spain. We determined the chemical composition of samples, allowing us to perform source apportionment using positive matrix factorization. The OP of PM was determined by measuring reactive oxygen species using dithiothreitol and ascorbic acid assays. Finally, to link the sources with the measured OP, both a Pearson's correlation and a multiple linear regression model were applied to the dataset. The results showed that in Barcelona, the OP of PM10 was much higher than those of PM2.5 and PM1, whereas in Montseny results for all PM sizes were in the same range, but significantly lower than in Barcelona. In Barcelona, several anthropogenic sources were the main drivers of OP in PM10 (Combustion + Road Dust + Heavy Oil + OC-rich) and PM2.5 (Road Dust + Combustion). In contrast, PM1 -associated OP was driven by Industry, with a much lower contribution to PM10 and PM2.5 mass. Meanwhile, Montseny exhibited no clear drivers for OP evolution, likely explaining the lack of a significant difference in OP between PM10, PM2.5, and PM1. Overall, this study indicates that size fraction matters for OP, as a function of the environment typology. In an urban context, OP is driven by the PM10 and PM1 size fractions, whereas only the PM1 fraction is involved in rural environments.

2011-2020 trends of urban and regional ammonia in and around Barcelona, NE Spain.

It is well established that in environments where NH3 abundance is limiting in secondary PM2.5 generation, a reduction of NH3 emissions can result in an important contribution to air quality control. However, as deduced from open data published by the European Environmental Agency, the availability of measurements of NH3 concentrations is very scarce, with very few countries in Europe reporting data consistently for extensive periods, this being especially true for urban background sites. In this framework, simultaneous multi-site measurements were carried out in NE (Northeast) Spain from 2011 to 2020, using diffusion tubes. The highest NH3 concentrations were recorded at the traffic site (5.3 µgm-3 on average), followed by those measured at the urban background site (2.1 µgm-3). Mean concentrations at the mountain site were 1.6 µgm-3, while the lowest concentrations were recorded at the regional site (0.9 µgm-3). This comparison highlights traffic emissions as an important source of NH3. A statistically significant time trend of this pollutant was observed at the urban background site, increasing by 9.4% per year. A season-separated analysis also revealed a significant increasing trend at the mountain site during summer periods, probably related with increasing emissions from agricultural/livestock activities. These increases in NH3 concentrations were hypothesized to be responsible for the lack of a decreasing trend of NO3- concentrations at the monitoring sites, in spite of a markedly reduction of NO2 during the period, especially at the urban background. Thus, this would in turn affect the effectiveness of current action plans to abate fine aerosols, largely made up of secondary compounds. Actions to reduce NH3 concentrations at urban backgrounds are challenging though, as predicting NH3 is subjected to a high uncertainty and complexity due to its dependence on a variety of factors. This complexity was clearly indicated by the application of a decision tree algorithm to find the parameters better predicting NH3 at the urban background under study. O3, NO, NO2, CO, SO2 and OM + EC concentrations, together with meteorological indicators, were used as independent variables, obtaining no combination of parameters evidently able to predict significant differences in NH3 concentrations, with a coefficient of determination between real and predicted measurements lower than 0.50. This emphasizes the need for highly temporally and spatially resolved NH3 measurements for an accurate design of abatement actions.

Understanding the local and remote source contributions to ambient O3 during a pollution episode using a combination of experimental approaches in the Guadalquivir valley, southern Spain.

The Guadalquivir Valley is one of three major O3 hotspots in Spain. An airborne and surface measurement campaign was carried out from July 9th to 11th, 2019 to quantify the local/regional O3 contributions using experimental approaches. Air quality and meteorology data from surface measurements, a microlight aircraft, a helium balloon, and remote sensing data (TROPOMI-NO2-ESA) were used to obtain the 3D distribution of O3 and various tracer pollutants. O3 accumulation over 2.5 days started with inputs from oceanic air masses transported inland by sea breezes, which drew O3 and its precursors from a local/regional origin to the northeastern end of the basin. The orographic-meteorological setting of the valley caused vertical recirculation of the air masses inside the valley that caused the accumulation by increasing regional background O3 concentration by 25-30 ppb. Furthermore, possible Mediterranean O3 contributions and additional vertical recirculation through the entrainment zone of the convective boundary layer also contributed. Using particulate matter finer than 2.5 µm (PM2.5), ultrafine particles (UFP), and black carbon (BC) as tracers of local sources, we calculated that local contributions increased regional O3 levels by 20 ppb inside specific pollution plumes transported by the breeze into the valley, and by 10 ppb during midday when flying over an area with abundant agricultural burning during the morning. Air masses that crossed the southern boundaries of the Betic system at mid-altitude (400-1850 m a.s.l.) on July 10th and 11th may have provided additional O3. Meanwhile, a decreasing trend at high altitudes (3000-5000 m a.s.l.) was observed, signifying that the impact of stratospheric O3 intrusion decreased during the campaign.

Quantifying traffic, biomass burning and secondary source contributions to atmospheric particle number concentrations at urban and suburban sites.

In this study, we propose a new approach to determine the contributions of primary vehicle exhaust (N1ff), primary biomass burning (N1bb) and secondary (N2) particles to mode segregated particle number concentrations. We used simultaneous measurements of aerosol size distribution in the 12-600 nm size range and black carbon (BC) concentration obtained during winter period at urban and suburban sites influenced by biomass burning (BB) emissions. As expected, larger aerosol number concentrations in the 12-25 and 25-100 nm size ranges are observed at the urban site compared to the suburban site. However, similar concentrations of BC are observed at both sites due to the larger contribution of BB particles to the observed BC at suburban (34%) in comparison to urban site (23%). Due to this influence of BB emissions in our study area, the application of the Rodríguez and Cuevas (2007) method, which was developed for areas mainly influenced by traffic emissions, leads to an overestimation of the primary vehicle exhaust particles concentrations by 18% and 26% in urban and suburban sites, respectively, as compared to our new proposed approach. The results show that (1) N2 is the main contributor in all size ranges at both sites, (2) N1ff is the main contributor to primary particles (>70%) in all size ranges at both sites and (3) N1bb contributes significantly to the primary particles in the 25-100 and 100-600 nm size ranges at the suburban (24% and 28%, respectively) and urban (13% and 20%, respectively) sites. At urban site, the N1ff contribution shows a slight increase with the increase of total particle concentration, reaching a contribution of up to 65% at high ambient aerosol concentrations. New particle formation events are an important aerosol source during summer noon hours but, on average, these events do not implicate a considerable contribution to urban particles.

Screened activity expansion for the grand potential of a quantum plasma and how to derive approximate equations of state compatible with electroneutrality.

We consider a quantum multicomponent plasma made with S species of point charged particles interacting via the Coulomb potential. We derive the screened activity series for the pressure in the grand-canonical ensemble within the Feynman-Kac path integral representation of the system in terms of a classical gas of loops. This series is useful for computing equations of state for it is nonperturbative with respect to the strength of the interaction and it involves relatively few diagrams at a given order. The known screened activity series for the particle densities can be recovered by differentiation. The particle densities satisfy local charge neutrality because of a Debye-dressing mechanism of the diagrams in these series. We introduce a new general neutralization prescription, based on this mechanism, for deriving approximate equations of state where consistency with electroneutrality is automatically ensured. This prescription is compared to other ones, including a neutralization scheme inspired by the Lieb-Lebowitz theorem and based on the introduction of (S-1) suitable independent combinations of the activities. Eventually, we briefly argue how the activity series for the pressure, combined with the Debye-dressing prescription, can be used for deriving approximate equations of state at moderate densities, which include the contributions of recombined entities made with three or more particles.

Evaluation of the Semi-Continuous OCEC analyzer performance with the EUSAAR2 protocol.

This work evaluates the applicability of the reference protocol EUSAAR2 in the Semi-Continuous OCEC analyzer under two environments, an urban background site influenced by traffic emissions and a regional background site. The comparison of the 24-h averaged OC and EC measurements of the Semi-Continuous analyzer with the OC and EC concentrations determined offline in PM2.5 24 h filters yielded very good agreement for both denuded and undenuded samples. In the urban background site, the regression for EC yielded a slope of 0.93 and 1.04 (b = 0.07 and 0.05, R2 = 0.83 and 0.84), for denuded and undenuded samples respectively. The slopes of OC regressions were 0.99 (b = -0.18, R2 = 0.81) for the low volume and 0.93 (b = 0.12, R2 = 0.84) for the high volume samples. In the regional background site, the slopes of the EC regression with the denuded and undenuded samples was 0.91 and 1.02 correspondingly (b = 0 and - 0.03, R2 = 0.77 and 0.89). The regression of OC had slopes close to 1; 1.03 for the high volume and 0.95 for the low volume sampler (b = 0.08 and 0.26, R2 = 0.78 and 0.78). BC measurements obtained by an aethalometer and MAAP were in very good agreement with EC at both sampling sites. BC levels were consistently higher than EC (slope of the regression aethalometer BC vs EC slope a = 1.2, intercept b = 0.19, R2 = 0.79, for the urban background site and a = 1.9, b = -0.04, R2 = 0.94, for the regional site, slope MAAP BC vs EC a = 1.2, b = 0.06, R2 = 0.94, for the urban background site and 1.7, b = -0.03, R2 = 0.96, for the regional site). This confirms the need of using the site-specific mass absorption cross section (MAC) instead of the ones provided by manufacturers for the conversion of absorption units into BC mass concentration. BC data correlated very well with the optical EC obtained from the semi-continuous OCEC analyzer (a = 1.3, b = 0.16, R2 = 0.80 for the urban background site and a = 1.7, b = 0.009, R2 = 0.94 for the regional site, respectively). The comparison of OC concentrations by the Semi-Continuous Sunset analyzer with organic aerosol online measurements by ACSM showed strong correlations. The ratio OA/OC was 1.9 and 2.3 for the urban background and regional sites. The accumulation of refractory material on the filter, because of prolonged periods of sampling, caused a shift of the split point to the inert mode and changes on PC formation and evolution. Extreme dust outbreaks lead to the overestimation of OC due to the evolution of carbonate in the He mode. Generally, the Sunset Semi-Continuous OCEC analyzer with EUSAAR2 provided robust and consistent measurements with offline thermal-optical analysis.

African dust and air quality over Spain: Is it only dust that matters?

The 2001-2016 contribution of African dust outbreaks to ambient regional background PM10 and PM2.5 levels over Spain, as well as changes induced in the PMx composition over NE Spain in 2009-2016, were investigated. A clear decrease in PMx dust contributions from the Canary Islands to N Iberia was found. A parallel increase in the PM2.5/PM10 ratio (30% in the Canary Islands to 57% in NW Iberia) was evidenced, probably due to size segregation and the larger relative contribution of the local PMx with increasing distance from Africa. PM1-10 and PM2.5-10 measured in Barcelona during African dust outbreaks (ADOs) were 43-46% higher compared to non-ADO days. The continental background contribution prevailed in terms of both PM1-10 and PM2.5-10 during ADO days (62 and 69%, respectively, and 31 and 27% for non-ADO days). The relative contributions of Al2O3/Fe2O3/CaO to PMx fraction showed that Al2O3 is a suitable tracer for African dust in our context; while CaO at the urban site is clearly affected by local resuspension, construction and road dust, and Fe2O3 by dust from vehicle brake discs. The results also provide evidence that PM increases during ADOs are caused not only by the mineral dust load, but by an increased accumulation of locally emitted or co-transported anthropogenic pollutants as compared with non-ADO days. Possible causes for this accumulation are discussed. We recommend that further epidemiological studies should explore independently the potential effects of mineral dust and the anthropogenic PM during ADOs, because, at least over SW Europe, not only mineral dust affects the air quality during African dust episodes.

Monitoring the impact of desert dust outbreaks for air quality for health studies.

We review the major features of desert dust outbreaks that are relevant to the assessment of dust impacts upon human health. Our ultimate goal is to provide scientific guidance for the acquisition of relevant population exposure information for epidemiological studies tackling the short and long term health effects of desert dust. We first describe the source regions and the typical levels of dust particles in regions close and far away from the source areas, along with their size, composition, and bio-aerosol load. We then describe the processes by which dust may become mixed with anthropogenic particulate matter (PM) and/or alter its load in receptor areas. Short term health effects are found during desert dust episodes in different regions of the world, but in a number of cases the results differ when it comes to associate the effects to the bulk PM, the desert dust-PM, or non-desert dust-PM. These differences are likely due to the different monitoring strategies applied in the epidemiological studies, and to the differences on atmospheric and emission (natural and anthropogenic) patterns of desert dust around the world. We finally propose methods to allow the discrimination of health effects by PM fraction during dust outbreaks, and a strategy to implement desert dust alert and monitoring systems for health studies and air quality management.

Vertical and horizontal fall-off of black carbon and NO2 within urban blocks.

While exposure to traffic pollutants significantly decreases with distance from the curb, very dense urban architectures hamper such dispersion. Moreover, the building height reduces significantly the dispersion of pollutants. We have investigated the horizontal variability of Black Carbon (BC) and the vertical variability of NO2 and BC within the urban blocks. Increasing the distance from road BC concentrations decreased following an exponential curve reaching halving distances at 25 m (median), although with a wide variability among sites. Street canyons showed sharper fall-offs than open roads or roads next to a park. Urban background concentrations were achieved at 67 m distance on average, with higher distances found for more trafficked roads. Vertical fall-off of BC was less pronounced than the horizontal one since pollutants homogenize quickly vertically after rush traffic hours. Even shallower vertical fall-offs were found for NO2. For both pollutants, background concentrations were never reached within the building height. A street canyon effect was also found exacerbating concentrations at the lowest floors of the leeward side of the road. These inputs can be useful for assessing population exposure, air quality policies, urban planning and for models validation.

Effectiveness of commercial face masks to reduce personal PM exposure.

Cycling and walking are promoted as means of transportation which can contribute to the reduction of traffic pollution in urban areas. However, cyclists and pedestrians may be exposed to high concentrations of air pollutants due to their proximity to vehicle emissions. Commercial face mask respirators are widely used, in both developing and developed countries, as an individual protective measure against particle pollution. However scientific data on the efficacy of face mask respirators in reducing airborne particle exposure is limited. In this study, a custom experimental set-up was developed in order to measure the effectiveness of nine different respirators under real environmental conditions in terms of particle mass concentration below 2.5 µm (PM2.5), particle number concentration (PNC), Lung Deposited Surface Area (LDSA) and Black Carbon concentration (BC). Face mask performances were assessed in a typical traffic affected urban background environment in the city of Barcelona under three different simulated breathing rates to investigate the influence of flow rate. Results showed a median face mask effectiveness for PM2.5 equal to 48% in a range of 14-96%, 19% in a range of 6%-61% for BC concentration, 19% in a range of 4%-63% for PNC and 22% in a range of 5%-65% for LDSA. For each pollutant under investigation, the best performance was found always with the same mask (N7) although it is not the most expensive (in a range of price of 1 to 44, its cost was 20 euros), which has a filter on the entire surface except for the 2 exhalation valves where air cannot enter but just exit and shows a good fit on the dummy head.

Particle-related exposure, dose and lung cancer risk of primary school children in two European countries.

Schools represent a critical microenvironment in terms of air quality due to the proximity to outdoor particle sources and the frequent lack of proper ventilation and filtering systems. Moreover, the population exposed in schools (i.e. children) represents a susceptible population due to their age. Air quality-based studies involving students' exposure at schools are still scarce and often limited to mass-based particle metrics and may thus underestimate the possible effect of sub-micron particles and particle toxicity. To this purpose, the present paper aims to evaluate the exposure to different airborne particle metrics (including both sub- and super-micron particles) and attached carcinogenic compounds. Measurements in terms of particle number, lung-deposited surface area, and PM fraction concentrations were measured inside and outside schools in Barcelona (Spain) and Cassino (Italy). Simultaneously, PM samples were collected and chemically analysed to obtain mass fractions of carcinogenic compounds. School time airborne particle doses received by students in classrooms were evaluated as well as their excess lung cancer risk due to a five-year primary school period. Median surface area dose received by students during school time in Barcelona and Cassino resulted equal to 110mm2 and 303mm2, respectively. The risk related to the five-year primary school period was estimated as about 2.9×10-5 and 1.4×10-4 for students of Barcelona and Cassino, respectively. The risk in Barcelona is slightly higher with respect to the maximum tolerable value (10-5, according to the U.S. Environmental Protection Agency), mainly due to toxic compounds on particles generated from anthropogenic emissions (mainly industry). On the other hand, the excess lung cancer risk in Cassino is cause of concern, being one order of magnitude higher than the above-mentioned threshold value due to the presence of biomass burning heating systems and winter thermal inversion that cause larger doses and great amount of toxic compounds on particles.

Outdoor and indoor particle characterization from a large and uncontrolled combustion of a tire landfill.

A large and uncontrolled fire of a tire landfill started in Seseña (Toledo, Spain) on May 13, 2016. An experimental deployment was immediately launched in the area for measuring regulated and non-standard air quality parameters to assess the potential impact of the plume at local and regional levels. Outdoor and indoor measurements of different parameters were carried out at a near school, approximately 700m downwind the burning tires. Real time measurements of ambient black carbon (BC) and total number particle concentrations were identified as good tracers of the smoke plume. Simultaneous peaks allowed us to characterize situations of the plume impact on the site. Outdoor total particle number concentrations reached in these occasions 3.8×105particlescm-3 (on a 10min resolution) whereas the indoor concentration was one order of magnitude lower. BC mass concentrations in ambient air were in the range of 2 to 7µgm-3, whereas concentrations<2µgm-3 were measured indoor. Indoor and outdoor deposited inhalable dust was sampled and chemically characterized. Both indoor and outdoor dust was enriched in tire components (Zn, sulfate) and PAHs associated to the tire combustion process. Infiltration processes have been documented for BC and particle number concentrations causing increases in indoor concentrations.

Spatial and temporal variability of carbonaceous aerosols: Assessing the impact of biomass burning in the urban environment.

Biomass burning (BB) is a significant source of atmospheric particles in many parts of the world. Whereas many studies have demonstrated the importance of BB emissions in central and northern Europe, especially in rural areas, its impact in urban air quality of southern European countries has been sparsely investigated. In this study, highly time resolved multi-wavelength absorption coefficients together with levoglucosan (BB tracer) mass concentrations were combined to apportion carbonaceous aerosol sources. The Aethalometer model takes advantage of the different spectral behavior of BB and fossil fuel (FF) combustion aerosols. The model was found to be more sensitive to the assumed value of the aerosol Ångström exponent (AAE) for FF (AAEff) than to the AAE for BB (AAEbb). As result of various sensitivity tests the model was optimized with AAEff=1.1 and AAEbb=2. The Aethalometer model and levoglucosan tracer estimates were in good agreement. The Aethalometer model was further applied to data from three sites in Granada urban area to evaluate the spatial variation of CMff and CMbb (carbonaceous matter from FF or BB origin, respectively) concentrations within the city. The results showed that CMbb was lower in the city centre while it has an unexpected profound impact on the CM levels measured in the suburbs (about 40%). Analysis of BB tracers with respect to wind speed suggested that BB was dominated by sources outside the city, to the west in a rural area. Distinguishing whether it corresponds to agricultural waste burning or with biomass burning for domestic heating was not possible. This study also shows that although traffic restrictions measures contribute to reduce carbonaceous concentrations, the extent of the reduction is very local. Other sources such as BB, which can contribute to CM as much as traffic emissions, should be targeted to reduce air pollution.

On the origin of the highest ozone episodes in Spain.

The 2000-2015 occurrences of the highest ozone (O3) pollution episodes in Spain were evaluated to investigate their origin. To this end, data series available for urban and regional background (UB and RB), traffic (TR) and industrial (IN) sites were analysed separately and intercompared. Results evidenced that during these 16years mean O3 levels in the RB sites did not change significantly, and remained constantly high. However, there is a clear increase at the TR and UB sites. Although sensitivity analysis is needed to interpret the cause of this increasing trend, this might be caused probably by the lower O3 titration intensity due to the preferential abatement of NO vs NO2, as supported from the neutral trend of OX (NO2+O3) at these sites. We found that the exceedances of the hourly information threshold for O3 (>180µg/m3) are recorded mostly at UB and IN sites located in seven areas of Spain (specific hotspots or at the tail end of large urban plumes), and that these increased during summer heatwaves (i.e. 2003 and 2015). Although the external contribution of regional-to-subcontinental transported O3 might be relevant during the highest O3 episodes in the Western Mediterranean, our results evidenced that in the above specific areas, regional-local O3 production decisively contributes to the exceedances of the information threshold. Also that the human protection threshold and the AOT40 are more frequently exceeded in the Central, Southern and Mediterranean sides of the Iberian Peninsula. The design of effective episode abatement measures is quite complex in those conditions, due to both the nonlinearity of the chemical processes of O3 formation and destruction, and to the interplay with the complex meteorological setting, causing frequent recirculation and in situ aging of air masses. However, the combination of meteorological forecasting of the main recirculation processes and sensitivity analysis of NOX/VOC emission abatement measures might be powerful tools to evaluate the effectiveness of potential O3 mitigation strategies. Finally we would like to highlight that the current UB, RB, IN and TR classification (somewhat subjective) is not adequate to interpret the origin of O3 exceedances in complex areas of Southern Europe. Thus, a UB station recording exceedances, and located in a small city in the tail end of an urban plume of a large city, receives not only the contribution from its own UB, but mainly from the specific high O3 RB caused by the urban plume transport.

Secondary organic aerosol origin in an urban environment: influence of biogenic and fuel combustion precursors.

Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 µg m(-3) from the first to the last sample.

An inter-comparison of PM10 source apportionment using PCA and PMF receptor models in three European sites.

Source apportionment of aerosol is an important approach to investigate aerosol formation and transformation processes as well as to assess appropriate mitigation strategies and to investigate causes of non-compliance with air quality standards (Directive 2008/50/CE). Receptor models (RMs) based on chemical composition of aerosol measured at specific sites are a useful, and widely used, tool to perform source apportionment. However, an analysis of available studies in the scientific literature reveals heterogeneities in the approaches used, in terms of "working variables" such as the number of samples in the dataset and the number of chemical species used as well as in the modeling tools used. In this work, an inter-comparison of PM10 source apportionment results obtained at three European measurement sites is presented, using two receptor models: principal component analysis coupled with multi-linear regression analysis (PCA-MLRA) and positive matrix factorization (PMF). The inter-comparison focuses on source identification, quantification of source contribution to PM10, robustness of the results, and how these are influenced by the number of chemical species available in the datasets. Results show very similar component/factor profiles identified by PCA and PMF, with some discrepancies in the number of factors. The PMF model appears to be more suitable to separate secondary sulfate and secondary nitrate with respect to PCA at least in the datasets analyzed. Further, some difficulties have been observed with PCA in separating industrial and heavy oil combustion contributions. Commonly at all sites, the crustal contributions found with PCA were larger than those found with PMF, and the secondary inorganic aerosol contributions found by PCA were lower than those found by PMF. Site-dependent differences were also observed for traffic and marine contributions. The inter-comparison of source apportionment performed on complete datasets (using the full range of available chemical species) and incomplete datasets (with reduced number of chemical species) allowed to investigate the sensitivity of source apportionment (SA) results to the working variables used in the RMs. Results show that, at both sites, the profiles and the contributions of the different sources calculated with PMF are comparable within the estimated uncertainties indicating a good stability and robustness of PMF results. In contrast, PCA outputs are more sensitive to the chemical species present in the datasets. In PCA, the crustal contributions are higher in the incomplete datasets and the traffic contributions are significantly lower for incomplete datasets.

Spatiotemporally resolved black carbon concentration, schoolchildren's exposure and dose in Barcelona.

At city level, personal monitoring is the best way to assess people's exposure. However, it is usually estimated from a few monitoring stations. Our aim was to determine the exposure to black carbon (BC) and BC dose for 45 schoolchildren with portable microaethalometers and to evaluate the relationship between personal monitoring and fixed stations at schools (indoor and outdoor) and in an urban background (UB) site. Personal BC concentra-tions were 20% higher than in fixed stations at schools. Linear mixed-effect models showed low R(2) between personal measurements and fixed stations at schools (R(2)  ≤ 0.28), increasing to R(2)  ≥ 0.70 if considering only periods when children were at schools. For the UB station, the respective R(2) were 0.18 and 0.45, indicating the importance of the distance to the monitoring station when assessing exposure. During the warm season, the fixed stations agreed better with personal measurements than during the cold one. Children spent 6% of their time on commuting but received 20% of their daily BC dose, due to co-occurrence with road traffic rush hours and the close proximity to the source. Children received 37% of their daily-integrated BC dose at school. Indoor environments (classroom and home) were responsible for the 56% BC dose.

Comment on "Direct linear term in the equation of state of plasmas".

In a recent paper [Phys. Rev. E 91, 013108 (2015)], Kraeft et al. criticize known exact results on the equation of state of quantum plasmas, which have been obtained independently by several authors. They argue about a difference in the definition of the direct two-body function Q(x), which appears in virial expansions of thermodynamical quantities, but Q(x) is not a measurable quantity in itself. Differences in definitions of intermediate quantities are irrelevant, and only differences in physical quantities are meaningful. Beyond Kraeft et al.'s broad statement that there is no agreement at order ρ(5/2) in the virial equation for the pressure, we show that their published results for this quantity are in fact in perfect agreement with previous existing expressions.

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.