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.

Indoor and outdoor concentrations and determinants of NO2 in a cohort of 1-year-old children in Valencia, Spain.

UNLABELLED: Nitrogen dioxide (NO2) is produced from the exhausts of vehicles and gas appliances and is known to pose certain health risks. In this study, we characterize the exposure to this substance during the first year of life, which is an important period of development. To this end, we used passive samplers to measure indoor and outdoor NO2 levels for 2 weeks in the homes of 352 children. To compensate for the fact that NO2 levels were measured only once in each home, a correction factor was calculated to assign each child an outdoor NO2 exposure value for the first year of life. The outdoor NO2 concentrations were 26.1 microg/m(3) while those measured indoors averaged 18.0 microg/m(3). A multivariate linear regression analysis showed that the main determinants of outdoor NO2 levels were the degree of urbanization and the frequency of vehicle traffic at the location of the residence while for indoor NO2 levels the principal determinants were the type of cooking range and water heater present in the home, the season of the year, and both the country of origin and educational level of the mother. PRACTICAL IMPLICATIONS: Exposure to NO2 has been related to respiratory and other health problems among children. Precise identification of the main sources of both indoor and outdoor NO2 should shed light on appropriate intervention periods and methods. Our results indicate that while population density and traffic-related variables are the main determinants of outdoor NO2 levels, the use of gas appliances have the greatest impact on indoor levels. Strategies should thus be developed to reduce such exposure, especially with regard to reducing emissions from vehicle traffic.

Photochemical model evaluation of the surface ozone impact of a power plant in a heavily industrialized area of southwestern Spain.

The characterization and evaluation of the impact that an industry is likely to have on the surrounding ozone levels is one of many problems confronting air quality managers and should be taken into consideration when authorizing its installation. The correct management of an environment, in terms of monitoring existing industries and planning new activities, requires adequate knowledge of the processes sustained by the industrial emissions therein. This paper explores the improvements in air quality management arising from taking into account the uncertainties involved in the photochemical modeling of the impact of an industry on surface ozone levels. For this, we evaluate the impact on ozone levels of a power plant located in an industrial area of southwestern Spain (Huelva). The evaluation takes into account the effects of both emissions' uncertainty and the non-linear chemistry between ozone and its precursors, thus providing a probable range of increase over the normative values (hourly and 8-hourly maximums) defined in the European Directive. The proposed methodology is easily applicable by air quality managers. Advanced modeling techniques were used for the power plant assessment, MM5 atmospheric modeling system, and air quality model CAMx. The results from meteorology and ozone forecasts have shown acceptable agreement with the observations. The spatial distribution of the impact is found to be strongly determined by mesoscale meteorological processes, which are reinforced by the local orography; there is also a marked temporal evolution. The industrial plume is observed to induce a decrease (or maintenance) of the ozone levels near the emission source (0-10km), and an increase in the ozone concentrations farther away (with maximums between 10 and 50km). In fact, in the meteorological episodes with a predominance of local breeze circulations, impacts have been detected at distances of more than 100km from the emission source. Sensitivity of the power plant impact to variations in ozone precursor emissions is described, and the scenarios and the points in the domain presenting higher sensitivity and registering larger impacts are also identified. The results show that the largest impacts take place in emission scenarios where the NO(x) has been reduced with respect to the base case scenario. In contrast, in scenarios where the VOC emissions are reduced with respect to the base case scenario, the impact is smaller or remains unchanged. This is important in areas like the study case, where there is a high percentage of biogenic VOC emissions and the industrial areas are close to natural protected areas and agricultural fields.

Combined approach for paediatric recurrent antrochoanal polyp: a single-centre case series of 27 children.

OBJECTIVE: To compare functional endoscopic sinus surgery with a combined approach (functional endoscopic sinus surgery plus Caldwell-Luc procedure) for the treatment of paediatric antrochoanal polyp, in terms of antrochoanal polyp recurrence and safety. METHOD: This retrospective case series comprises 27 paediatric patients with recurrent antrochoanal polyp, treated from January 2010 to January 2018. RESULTS: The average age of the patients at the time of diagnosis was 10.4 ± 2.49 years. The recurrence rate after functional endoscopic sinus surgery alone was 72.9 per cent, compared with 12.5 per cent after functional endoscopic sinus surgery plus the Caldwell-Luc procedure (p < 0.00001). No complications were reported during surgery or follow up. CONCLUSION: The correct identification of the origin of the antrochoanal polyp and an adequate returning of maxillary ventilation by widening the ostium can prevent recurrences. Although functional endoscopic sinus surgery continues to be the 'gold standard' for antrochoanal polyp treatment, in cases of revision surgery, a combined approach could ensure the complete removal of the polyp through the two openings.

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.

New classification scheme for ozone monitoring stations based on frequency distribution of hourly data.

According to European Union (EU) legislation, ozone (O3) monitoring sites can be classified regarding their location (rural background, rural, suburban, urban) or based on the presence of emission sources (background, traffic, industrial). There have been attempts to improve these classifications aiming to reduce their ambiguity and subjectivity, but although scientifically sound, they lack the simplicity needed for operational purposes. We present a simple methodology for classifying O3 stations based on the characteristics of frequency distribution curves which are indicative of the actual impact of combustion sources emitting NO that consumes O3 via titration. Four classes are identified using 1998-2012 hourly data from 72 stations widely distributed in mainland Spain and the Balearic Islands. Types 1 and 2 present unimodal bell-shaped distribution with very low amount of data near zero reflecting a limited influence of combustion sources while Type 4 has a primary mode close to zero, showing the impact of combustion sources, and a minor mode for higher concentrations. Type 3 stations present bimodal distributions with the main mode in the higher levels. We propose a quantitative metric based on the Gini index with the objective of reproducing this classification and finding empirical ranges potentially useful for future classifications. The analysis of the correspondence with the EUROAIRNET classes for the 72 stations reveals that the proposed scheme is only dependent on the impact of combustion sources and not on climatic or orographic aspects. It is demonstrated that this classification is robust since in 87% of the occasions the classification obtained for individual years coincide with the global classification obtained for the 1998-2012 period. Finally, case studies showing the applicability of the new classification scheme for assessing the impact on O3 of a station relocation and performing a critical evaluation of an air quality monitoring network are also presented.

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.

Presence of secretory IgA in human periapical lesions.

The concentration of secretory IgA in fluids present in the canals of 33 teeth was determined by the rocket immunoelectrophoresis technique. Except for the presence or absence of communication between the oral cavity and the root canals of the affected teeth, no other clinical finding showed significant statistical correlation with the presence of secretory IgA. The canals which were open to the oral flora had significantly higher concentrations of secretory IgA. Leaving canals open to the oral cavity may result in formation of periapical cysts.

Levels of particulate matter in rural, urban and industrial sites in Spain.

This paper summarises the results of a series of studies on the interpretation of time series of levels of total suspended particles (TSP) and particulate matter (PM, <10 microm) in six regions of Spain in the period 1996-2000. In addition to the local pollution events, high PM10 episodes are recorded during African dust outbreaks, regional atmospheric recirculation events (mainly in spring to autumn), and to a lesser extent, under the influence of European and Mediterranean long range transported air masses. The lowest PM10 levels are usually recorded under Atlantic air mass advective conditions. All these regional and large-scale processes account for the relatively high PM10 levels recorded in regional background stations in Spain. Thus, the PM10 levels recorded at EMEP (Cooperative Program for Monitoring and Evaluation of the Long Range Transmission of Air Pollutants in Europe) regional background stations between March 2001 and March 2002 are very close to the annual limit value proposed for 2010 by the EU Air Quality Directive 1999/30/CE. Chemical data obtained for the different monitoring stations during 2001 show a high mineral load in PM10 for most of the study sites in Spain. Furthermore, a high marine aerosol load is evidenced in the Canary Islands. These mineral and marine loads are lower when considering PM2.5, but a relatively high proportion (8-21%) of mineral dust is still present.

Impacts on particles and ozone by transport processes recorded at urban and high-altitude monitoring stations.

In order to evaluate the influence of particle transport episodes on particle number concentration temporal trends at both urban and high-altitude (Aitana peak-1558 m a.s.l.) stations, a simultaneous sampling campaign from October 2011 to September 2012 was performed. The monitoring stations are located in southeastern Spain, close to the Mediterranean coast. The annual average value of particle concentration obtained in the larger accumulation mode (size range 0.25-1 µm) at the mountain site, 55.0 ± 3.0 cm(-3), was practically half that of the value obtained at the urban station (112.0 ± 4.0 cm(-3)). The largest difference between both stations was recorded during December 2011 and January 2012, when particles at the mountain station registered the lowest values. It was observed that during urban stagnant episodes, particle transport from urban sites to the mountain station could take place under specific atmospheric conditions. During these transports, the major particle transfer is produced in the 0.5-2 µm size range. The minimum difference between stations was recorded in summer, particularly in July 2012, which is most likely due to several particle transport events that affected only the mountain station. The particle concentration in the coarse mode was very similar at both monitoring sites, with the biggest difference being recorded during the summer months, 0.4 ± 0.1cm(-3) at the urban site and 0.9 ± 0.1cm(-3) at the Aitana peak in August 2012. Saharan dust outbreaks were the main factor responsible for these values during summer time. The regional station was affected more by these outbreaks, recording values of >4.0 cm(-3), than the urban site. This long-range particle transport from the Sahara desert also had an effect upon O3 levels measured at the mountain station. During periods affected by Saharan dust outbreaks, ozone levels underwent a significant decrease (3-17%) with respect to its mean value.

Binding of Co(III) to a DNA oligomer via reaction of [Co(NH3)5(OH2)]3+ with (5medC-dG)4.

The interaction specificities of cobalt(III) ammines with the self-complementary eight-base pair DNA oligomer (5medC-dG)4 have been investigated. Standard protocol for preparing DNA samples calls for heat annealing the DNA oligomer in phosphate buffer in the absence or presence of cobalt(III) ammine complex for 2 min at 80 degrees C, followed by slow cooling to 25 degrees C. An alternative method for DNA preparation is incubation of the oligomer in the presence of the cobalt(III) complex at 37 degrees C followed by exhaustive dialysis. The conformational properties of the thus-treated DNA oligomer were determined by inspection of the UV and CD spectra at 25 and 95 degrees C and thermal denaturation studies. With heat annealing in the absence of any cobalt(III) complex, (5medC-dG)4 assumes a double-stranded, right-handed B conformation at 25 degrees C. Upon heat annealing in the presence of 200 microM [Co(NH3)6]3+, (5medC-dG)4 assumes a double-stranded, left-handed Z conformation at 25 degrees C. In contrast, the CD and UV spectra of (5medC-dG)4 heat annealed in the presence of 200 microM [Co(NH3)5(OH2)]3+ are consistent with a distorted B-like conformation at 25 degrees C. Incubation of the oligomer in the presence of [Co(NH3)5(OH2)]3+ results in modification of the conformational properties of the oligomer at both 25 and 95 degrees C relative to the untreated oligomer. The extent of modification depends upon the incubation concentration of [Co(NH3)5-(OH2)]3+ and the reaction time. Atomic absorption (AA) analyses of these treated DNA samples indicate a high degree of cobalt association to the oligomer.(ABSTRACT TRUNCATED AT 250 WORDS)