Surface ozone trends at El Arenosillo observatory from a new perspective.

Surface ozone trends observed at El Arenosillo observatory for the last 22 years (2000-2021) were investigated. The trends for daily averages and daily 5th and 95th percentiles were 1.2 ± 0.3 ppb decade-1, 2.2 ± 0.3 ppb decade-1 and -0.03 ± 0.43 ppb decade-1, respectively, thus showing a significant increase of background ozone. The surface temperature trends were also explored, obtaining trends of 0.5 ± 0.2 °C decade-1, 1.1 ± 0.2 °C decade-1 and -0.3 ± 0.2 °C decade-1 for daily averages, 5th and 95th percentiles, respectively. To identify potential changes in the ozone drivers, the weather pattern shifts were analyzed through the horizontal distribution trends of temperature at 2 m and geopotential height at 850 hPa. A strengthening of the Azores anticyclone and a regional warming were detected, which could contribute to the ozone trends obtained. The surface ozone trend in every month was explored, identifying a monthly pattern, with remarkable opposite trends in December-January (2.4 ± 0.9 ppb decade-1) vs July-August (-0.5 ± 1.1 ppb decade-1). The surface ozone trends for every hour of the day were also explored, identifying two clear patterns. The first pattern occurred from spring to autumn and was characterized by a behavior opposite to the typical daily ozone cycle. The second pattern was observed in winter, and it shows two relative peaks in the ozone trends (around 13:00 and 19:00 UTC). In a context of ozone precursor's depletion, changes in the weather conditions and warmer climate, to improve our knowledge of the ozone trends, we suggest exploring them based on daily and hourly averages.

Morphological and Optical Characterization of Gold Nanoparticles Decorated Porous Silicon.

In this article, physical characteristics of porous silicon (PS) obtained by electro chemical etching using HAuCl4 in the electrolyte are described. The morphological and optical features of PS decorated with gold-nanoparticles (AuNPs) were analyzed in function of the chemical etching time. The insertion of AuNPs inside the PS were performed simultaneously with the formation of the porous silicon layer. Scanning electron microscopy (SEM) analysis showed the formation and incorporation of AuNPs with an average size of 20 nm in the PS structure, which has a pore size of 1.5 µm. Also, it was possible to observe the loss of Si in function of the etching time. Photoluminescence spectroscopy analysis shows a decreasing of the PL intensity, which can be related to the presence of oxygen in the samples. Raman spectroscopy was used to estimate the size of the Si nanocrystals in the PS structure, which suffers a reduction in size due to the presence of HAuCl4 in the electrolyte.

Evaluation of Nanomechanical Properties of Tomato Root by Atomic Force Microscopy.

Here, different tissue surfaces of tomato root were characterized employing atomic force microscopy on day 7 and day 21 of growth through Young's modulus and plasticity index. These parameters provide quantitative information regarding the mechanical behavior of the tomato root under fresh conditions in different locations of the cross-section of root [cell surface of the epidermis, parenchyma (Pa), and vascular bundles (Vb)]. The results show that the mechanical parameters depend on the indented region, tissue type, and growth time. Thereby, the stiffness increases in the cell surface of epidermal tissue with increasing growth time (from 9.19 ± 0.68 to 13.90 ± 1.68 MPa) and the cell surface of Pa tissue displays the opposite behavior (from 1.74 ± 0.49 to 0.48 ± 0.55); the stiffness of cell surfaces of Vb tissue changes from 10.60 ± 0.58 to 6.37 ± 0.53 MPa, all cases showed a statistical difference (p < 0.05). Viscoelastic behavior dominates the mechanical forces in the tomato root. The current study is a contribution to a better understanding of the cell mechanics behavior of different tomato root tissues during growth.

Spatial and temporal variation of surface ozone, NO and NO2 at urban, suburban, rural and industrial sites in the southwest of the Iberian Peninsula.

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO(x) = NO + NO2), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO2 concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO(x)) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO2 concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00-17:00 UTC) while for NOx two peaks were observed, at 7:00-10:00 UTC and 20:00-22:00. In the case of rural stations, no hourly peak of ozone or NO(x) was registered. The weekend effect was studied by using a statistical contrast tests (Student's t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO2, whereas an ozone weekend effect was not detected in any case.

Occupational exposures in two industrial plants devoted to the production of ammonium phosphate fertilisers.

In order to fill a gap in the open literature, occupational exposures and activity concentrations have been assessed in two NORM industrial plants, located in the south-west of Spain, devoted to the production of mono-ammonium phosphate (MAP) and di-ammonium phosphate (DAP) fertilisers. The annual effective doses received by the workers from these plants are clearly below 1 mSv yr(-1) and the contribution due to external radiation is similar to that due to inhalation. The contribution to the maximum effective doses due to inhalation of particulate matter has been estimated to be about 0.12 mSv yr(-1), while the (222)Rn concentrations inside the plants are of no concern. Consequently, no additional actions or radiological protection measures need to be taken to decrease the natural radiation received by the workers in these facilities.

Study of the properties of ZnO:Zn thin films obtained from ZnO/Zn/ZnO structure deposited by DC sputtering.

A method to manage the resistivity of n-type ZnO films is presented. It involves the controlled diffusion of Zn at low temperature in N2 atmosphere into the ZnO/Zn/ZnO structure. The structures were made by DC sputtering technique. The diffusion periods were varied from 5 to 30 min. This process allow us to obtain ZnO films with excess of Zn (ZnO:Zn). The electrical characterization showed that the resistivity of the films can be varied from 0.01 to 100 omega-cm, the electron concentration from 10(19) to 10(17) cm(-3) and the carrier mobility from 10 to 40 cm2N-s. The films are nanocrystalline with preferred (002) orientation and crystal size that varies from 13 to 20 nm depending on the diffusion period. The films have a band gap of 3.18 eV and 70% of transmittance in the visible region, these properties were obtained from the transmittance measurements of low-resistivity films. Films have good structural, optical and electrical properties, and could be used in the manufacture of light emitting diodes.

Radon transport events associated with the impact of a NORM repository in the SW of Europe.

Two radon measurement stations located to the north and south of a NORM (Naturally Occurring Radioactive Materials) repository of phosphogypsum (southwest of Europe) were used to monitor radon behavior during 2018. The stations are located at opposing sides of the repository, one in Huelva City to the north and other one in a rural area to the south. This setup aimed to identify the influence of the NORM repository on each station and use radon levels as a marker of atmospheric transport in the local area. To achieve this, a comparison was carried out with other coastal stations in the south of Spain, finding higher average concentrations in Huelva City, ~3.3 Bq m-3. Hierarchical clustering was applied to identify days with different radon patterns at each Huelva station, detecting possible local radon transport events from the repository. Three events were investigated with WRF (Weather Research and Forecasting) and FLEXPART-WRF (FLEXible PARTicle dispersion model). It was found that both sampling sites required atmospheric stagnant conditions to reach high radon concentration. However, under these conditions the urban station showed high radon regardless of wind direction while the rural station also required radon transport from the repository, either directly or indirectly.

Recent and historical pollution legacy in high altitude Lake Marboré (Central Pyrenees): A record of mining and smelting since pre-Roman times in the Iberian Peninsula.

We have analyzed potential harmful trace elements (PHTE; Pb, Hg, Zn, As and Cu) on sediment cores retrieved from lake Marboré (LM) (2612 m a.s.l, 42°41'N; 0° 2'E). PHTE variability allowed us to reconstruct the timing and magnitude of trace metal pollutants fluxes over the last 3000 years in the Central Pyrenees. A statistical treatment of the dataset (PCA) enabled us to discern the depositional processes of PHTE, that reach the lake via direct atmospheric deposition. Indeed, the location of LM above the atmospheric boundary layer makes this lake an exceptional site to record the long-range transport of atmospheric pollutants in the free troposphere. Air masses back-trajectories analyses enabled us to understand the transport pathways of atmospheric pollutants while lead isotopic analyses contributed to evaluate the source areas of metal pollution in SW Europe during the Late Holocene. PHTE variability, shows a clear agreement with the main exploitation phases of metal resources in Southern Europe during the Pre-Industrial Period. We observed an abrupt lead enrichment from 20 to 375 yrs CE mostly associated to silver and lead mining and smelting practices in Southern Iberia during the Roman Empire. This geochemical data suggests that regional atmospheric metal pollution during the Roman times rivalled the Industrial Period. PHTE also increased during the High and Late Middle Ages (10-15th centuries) associated to a reactivation of mining and metallurgy activities in high altitude Pyrenean mining sites during climate amelioration phases. Atmospheric mercury deposition in the Lake Marboré record mostly reflects global emissions, particularly from Almadén mines (central Spain) and slightly fluctuates during the last three millennia with a significant increase during the last five centuries. Our findings reveal a strong mining-related pollution legacy in alpine lakes and watersheds that needs to be considered in management plans for mountain ecosystems as global warming and human pressure effects may contribute to their future degradation.

Ground-based and OMI-TROPOMI NO2 measurements at El Arenosillo observatory: Unexpected upward trends.

Eleven years, January 2008 to June 2019, of hourly nitrogen dioxide (NO2) levels recorded at El Arenosillo observatory (Southwestern Europe) were analyzed. Annual averages ranged between 4 µg m-3 and 6 µg m-3 with peaks exceeding 40 µg m-3. A slight monthly variation was observed with maximum and minimum values in the cold (∼6 µg m-3) and warm (∼4 µg m-3) seasons respectively. A diurnal pattern was found with a weak amplitude (∼3 µg m-3). The monthly trends were investigated using surface observations and OMI (Ozone Monitoring instrument) satellite measurements. An unexpected upward trend was obtained in the last five years. The periods with elevated NO2 concentrations in the last years were analyzed, showing an increase in its frequency and concentrations, linked with the upward trend observed. The weather conditions in these NO2 peaks were studied using local surface meteorology, mean sea level pressure and wind fields from the data reanalysis of ERA5. The transport of NO2 was explored using TROPOMI (Tropospheric Monitoring Instrument) measurements. The events occurred under conditions governed by high-pressure systems, which induced weak synoptic airflows or the development of mesoscale processes. Four scenarios of NO2 transport were identified, associated with weak synoptic flows from inland or Southern Portugal and with mesoscale processes. The gulf of Cadiz plays an important role as a reservoir where the NO2 coming from the south of Portugal, the Western Mediterranean Basin and urban-industrial areas can be accumulated and later transported inland. A strong correlation was found between the increase of NO2 observed in the last years and positive anomalies of the temperature and geopotential height at 850 and 500 hPa levels. These findings could indicate that the causes of the changes in the NO2 would be attributed to alterations in the weather patterns associated with a warmer climate.

SO2 measurements in a clean coastal environment of the southwestern Europe: Sources, transport and influence in the formation of secondary aerosols.

Two years of SO2 measurements at El Arenosillo observatory located in the Gulf of Cadiz (Atlantic Ocean) were investigated. Annual hourly averages of 1.9 ± 1.5 µg m-3 and p95 between 3 and 4.4 µg m-3 were recorded, showing clean and background environments. Monthly means vary between 1.5 and 2.4 µg m-3, a monthly evolution was not found. SO2 fields from the MERRA2 model were used to identify SO2 sources and its transport, which could be affecting the studied region. Although SO2 records were low, major conductive for SO2 increases were observed in specific periods. A selection methodology was applied to extract these events, which showed a mean of ~11 µg m-3. Surface meteorological observations and ERA5 meteorological fields from the ECMWF model were used to assess the weather conditions. SO2 increases, in cold months occurred under conditions governed by synoptic-scale. Two types of transport scenarios were identified: SO2 transport defined as direct impact, which is the sum of the plumes from Portugal and the Huelva area; and indirect impact, where SO2 and sulphate particle emissions from Portugal were transported and accumulated in the Gulf of Cadiz and then carried inland, where new particle formation were observed. Episodes with high SO2 concentrations were also reported in warm periods associated with pure sea-land breezes. The SO2 peaks under sea-land breezes were associated with the transport of SO2 from the south of Portugal to the Gulf of Cadiz, whereas SO2 from the east of the Iberian Peninsula and north of Africa reached the Mediterranean Sea and were then transported to the Atlantic Ocean following the Strait of Gibraltar. Blocking of the airflows from the Mediterranean Sea to the Atlantic Ocean turns the Gulf of Cadiz into a chemical reservoir, where chemical species such as SO2 can accumulate, triggering new particle formation processes.

Influence of the accumulation chamber insertion depth to measure surface radon exhalation rates.

A common method to measure radon exhalation rates relies on the accumulation chamber technique. Usually, this approach only considers one-dimensional gas transport within the soil that neglects lateral diffusion. However, this lateral transport could reduce the reliability of the method. In this work, several cylindrical-shaped accumulation chambers were built with different heights to test if the insertion depth of the chamber into the soil improves the reliability of the method and, in that case, if it could limit the radon lateral diffusion effects. To check this hypothesis in laboratory, two reference exhalation boxes were manufactured using phosphogypsum from a repository located nearby the city of Huelva, in the southwest of Spain. Laboratory experiments showed that insertion depth had a deep impact in reducing the effective decay constant of the system, extending the interval where the linear fitting can be applied, and consistently obtaining reliable exhalation measurements once a minimum insertion depth is employed. Field experiments carried out in the phosphogypsum repository showed that increasing the insertion depth could reduce the influence of external effects, increasing the repeatability of the method. These experiments provided a method to obtain consistent radon exhalation measurements over the phosphogypsum repository.

Recent increase in NO2 levels in the southeast of the Iberian Peninsula.

We report the evolution of tropospheric NO2 over the south-east of the Iberian Peninsula from 2005 to 2017. We have used hourly NO2 levels measured at air-quality stations in urban and suburban environments. Annual averages ranged between 14 and 45 µg m-3, with peaks above 200 µg m-3. A monthly variation was observed, with higher concentrations in cold months (40-60 µg m-3) and lower levels in the warm season (13-17 µg m-3). A diurnal pattern was found in urban and suburban areas. The upward trend in NO2 observed during the whole period contrasts with the upward trend reported in 2013-2017. The NO2 tropospheric column levels measured by the Ozone Monitoring Instrument over the Iberian Peninsula indicated a similar behaviour; nevertheless, the largest Spanish metropolitan areas did not show this increase. The mean sea level pressure and wind field data of ERA5 (European Centre for Medium-Range Weather Forecasts) were used to investigate the weather conditions, the NO2 outputs of the Copernicus Monitoring Services being used for the assessment of the NO2 spatial distribution. NO2 regional events, with concentrations in the range 140-150 µg m-3, and which occurred both in the winter and summer season under anticyclonic conditions, are also described. A local origin is identified in winter, whereas in summer, they are associated with a high-pressure system that blocks Mediterranean outflows towards the Atlantic Ocean. The high NO2 levels are attributed mainly to two factors: i) local emissions, rather than contributions from the western Mediterranean (or even North Africa), and ii) an increase in the pressure gradient between the Atlantic and the Mediterranean pressure systems, associated with a decrease in wind speed, was found during the last five years compared with the previous eight. Meteorological and chemical changes in mid-latitudes associated with global warming should also be investigated in the future.

Dataset of the synthesis parameters to deposit YSZ on stainless steel AISI 316L by sputtering technique.

The data presented in this article are related to the research previously published "improvement of adhesion and barrier properties of biomedical stainless steel by deposition of YSZ coatings using RF magnetron sputtering". It contains the structural, morphological, compositional and electrochemical characterization of bare AISI 316L substrate which was used as a substrate to coat with yttria-stabilized zirconia (YSZ). The chemical composition and topography analyses from X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and micrographs from atomic force microscopy (AFM) as well as the roughness value of the YSZ-sputtered coating on AISI 316L substrates are presented as complementary data of the article.

Study of the exceptional meteorological conditions, trace gases and particulate matter measured during the 2017 forest fire in Doñana Natural Park, Spain.

In late June 2017, a forest fire occurred in Doñana Natural Park, which is located in southwestern Europe. Many animal and plant species, some of which are threatened, suffered from the impact of this fire, and important ecosystems in the European Union were seriously affected. This forest fire occurred under exceptional weather conditions. The meteorological situation was studied at both the synoptic scale and the local scale using meteorological fields in the ERA-Interim global model from ECMWF (European Centre for Medium Range Weather Forecasts), the WRF (Weather Research and Forecasting) mesoscale model and ground observations collected at El Arenosillo observatory. Anomalies were obtained using records (observations and simulations) over the last two decades (1996-2016). An anticyclonic system dominated the synoptic meteorological conditions, but a strong pressure gradient was present; positive high pressure anomalies and negative low pressure anomalies resulted in intense NW flows. At the surface, wind gusts of 80 km h-1, temperatures up to 35 °C and relative humidity values <20% were observed. In terms of anomalies, these observations corresponded to positive temperature anomalies (differences of 12 °C), positive wind speed anomalies (>29 km h-1) and negative relative humidity anomalies (differences of 40%). The forest fire reached El Arenosillo observatory approximately 8 h after it began. When the fire started, record-setting maximum values were measured for all gases monitored at this site (specifically, peaks of 99,995 µg m-3 for CO, 951 µg m-3 for O3, 478 µg m-3 for NO2, 116 µg m-3 for SO2 and 1000 µg m-3 for PM10). According to the temporal evolution patterns of these species, the atmosphere over a burnt area can recover to initial atmospheric levels between 48 and 96 h after an event. The impact of the Doñana plume was studied using hourly forward trajectories computed with the HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory) model to analyse the emission source for the burnt area. The Doñana fire plume affected large metropolitan areas near the Mediterranean coast. Air quality stations located in the cities of Seville and Cadiz registered the arrival of the plume based on increases in CO and PM10. Using CO as a tracer, measurements from the AIRS and MOPITT instruments allowed us to observe the transport of the Doñana plume from the Strait of Gibraltar to the Mediterranean. Finally, after two days, the Doñana forest fire plume reached the western Mediterranean basin.

An anomalous African dust event and its impact on aerosol radiative forcing on the Southwest Atlantic coast of Europe in February 2016.

A desert dust (DD) event that had its origin in North Africa occurred on the 20th-23rd of February 2016. The dust transport phenomenon was exceptional because of its unusual intensity during the coldest season. A historical dataset (2006-2015) of February meteorological scenarios using ECMWF fields, meteorological parameters, aerosol optical properties, surface O3 and AOD retrieved from MODIS at the El Arenosillo observatory (southwestern Spain) were analysed and compared with the levels during the DD event to highlight its exceptionality. Associated with a low-pressure system in western North Africa, flows transported air from the Sahel to Algeria and consequently increased temperatures from the surface to 700hPa by up to 7-9°C relative to the last decade. These conditions favoured the formation of a Saharan air layer. Dust was transported to the north and reached the Western Mediterranean Basin and the Iberian Peninsula. The arrival of the DD event at El Arenosillo did not affect the surface weather conditions or ozone but did impact the aerosol radiative forcing at the top of atmosphere (RFTOA). Aerosol radiative properties did not change relative to historical; however, the particle size and the amount of the aerosol were significantly higher. The DD event caused an increase (in absolute terms) of the mean aerosol RFTOA to a value of -8.1Wm-2 (long-term climatological value ~-1.5Wm-2). The aerosol RFTOA was not very large relative other DD episodes; however, our analysis of the historical data concluded that the importance of this DD event lay in the month of occurrence. European phenological datasets related to extreme atmospheric events predominantly reflect changes that are probably associated with climate change. This work is an example of this phenomenon, showing an event that occurred in a hotspot, the Saharan desert, and its impact two thousand km away.

Unexpected increase in the oxidation capacity of the urban atmosphere of Madrid, Spain.

Atmospheric oxidants such as ozone (O3), hydroxyl and nitrate radicals (OH and NO3) determine the ability of the urban atmosphere to process organic and inorganic pollutants, which have an impact on air quality, environmental health and climate. Madrid city has experienced an increase of 30-40% in ambient air O3 levels, along with a decrease of 20-40% in NO2, from 2007 to 2014. Using air pollution observations and a high-resolution air quality model, we find a large concentration increase of up to 70% and 90% in OH and NO3, respectively, in downtown Madrid (domain-wide average increase of 10% and 32% for OH and NO3, respectively). The results also show an 11% reduction in the nitric acid concentrations, leading to a remarkable denoxification of this urban atmosphere with implications for lower PM2.5 levels and nitrogen input into ecosystems. This study suggests that projected worldwide NOx emission reductions, following air quality standards, will lead to important changes in the oxidizing capacity of the atmosphere in and around large cities.

Analysis of the vertical radon structure at the Spanish "El Arenosillo" tower station.

This paper presents an analysis of one year of hourly radon and meteorological measurements at 10 m and 100 m a.g.l. at El Arenosillo tall-tower station, in the south-west of the Iberian Peninsula. Whole-year and seasonal composites of the diurnal radon cycle show the expected behaviour, with larger concentrations at 10 m than at 100 m during the night, due to poor vertical mixing, and similar concentrations at both heights during the daylight hours. Wind speed and wind direction analyses by sector show the prevailing contributions for each season. Sectors with air which has spent a longer period over the ocean and high wind speeds will lead to low concentrations at both levels, whereas inland sectors show a clear increase of the concentrations with similar overall averages for the two levels. The Sierra Morena, Guadalquivir and Bethics System sectors (continental pathways) are the sectors that show higher concentrations for mild to large wind speeds. The daily evolution of radon concentration differences at both heights has been grouped into four clusters by using a K-means algorithm method. The four clusters have been selected so that they sufficiently describe different characteristics in terms of stability. The temporal evolution of the mixing height (MH) and of the bulk diffusivity parameter (Kb) during the nocturnal period has been calculated by using the temporal variation of (222)Rn concentration at 10 m and the concentration gradient with height, respectively.

A long-term study of new particle formation in a coastal environment: meteorology, gas phase and solar radiation implications.

New particle formation (NPF) was investigated at a coastal background site in Southwest Spain over a four-year period using a Scanning Particle Mobility Sizer (SMPS). The goals of the study were to characterise the NPF and to investigate their relationship to meteorology, gas phase (O3, SO2, CO and NO2) and solar radiation (UVA, UVB and global). A methodology for identifying and classifying the NPF was implemented using the wind direction and modal concentrations as inputs. NPF events showed a frequency of 24% of the total days analysed. The mean duration was 9.2±4.2 h. Contrary to previous studies conducted in other locations, the NPF frequency reached its maximum during cold seasons for approximately 30% of the days. The lowest frequency took place in July with 10%, and the seasonal wind pattern was found to be the most important parameter influencing the NPF frequency. The mean formation rate was 2.2±1.7 cm(-3) s(-1), with a maximum in the spring and early autumn and a minimum during the summer and winter. The mean growth rate was 3.8±2.4 nm h(-1) with higher values occurring from spring to autumn. The mean and seasonal formation and growth rates are in agreement with previous observations from continental sites in the Northern Hemisphere. NPF classification of different classes was conducted to explore the effect of synoptic and regional-scale patterns on NPF and growth. The results show that under a breeze regime, the temperature indirectly affects NPF events. Higher temperatures increase the strength of the breeze recirculation, favouring gas accumulation and subsequent NPF appearance. Additionally, the role of high relative humidity in inhibiting the NPF was evinced during synoptic scenarios. The remaining meteorological variables (RH), trace gases (CO and NO), solar radiation, PM10 and condensation sink, showed a moderate or high connection with both formation and growth rates.

Physical and structural characterisation of zein and chitosan edible films using nanotechnology tools.

The use of composite edible films made from biopolymers has attracted interest as a way to reduce pollution and recycling problems; however, the relation between barrier, mechanical and structural properties of the films have been scarcely studied. The aim of this work was to evaluate composite zein-chitosan edible films by applying common nanotechnology tools and to relate the results to zein concentration and film structural changes. Rougher, more elastic, and less hard film structures with better water vapour barrier properties were obtained using larger zein concentrations. Raman spectroscopy exhibited unexpected interactions, as indicated by the disappearance of the thiol groups of cysteine in the zein films and the appearance of O=S=O and C-O-S groups in the blended materials in conjunction with the disappearance of zein ε-amino and -NH2 functional groups in the zein film samples, thereby confirming changes in the blended film structure. Zein concentration presented linear correlations with water vapour permeability (R=-0.978) and film roughness (R=0.929). The composite films presented better barrier and mechanical properties than single ingredient films. This information shows the benefit of using protein-polysaccharide blends to prepare edible films.

Application of cluster analysis to surface ozone, NO2 and SO2 daily patterns in an industrial area in Central-Southern Spain measured with a DOAS system.

The daily variations of surface ozone, NO2 and SO2 have been investigated in a heavily industrialised area in the centre of the Iberian Peninsula (Puertollano) using hourly values recorded during two years (2008-2009) with an active LP-DOAS system. The meteorological conditions and air masses have been studied using the HYSPLIT model. The maximum hourly levels of these air pollutants exceeded 100 ppb for ozone, 150 ppb for SO2 and 210 ppb for NO2. However, mean values for ozone, NO2 and SO2 were of 49, 10 and 3 ppb respectively. Daily-monthly evolutions (defined as daily evolutions for different months) have been analysed in order to know the general daily behaviour of these species. Air pollution problems have been identified using the thresholds defined in the European Directive 2008. The limits to protect human health (human health protection limitations) have been exceeded during the study period. In order to find a set of representative daily cycles for each pollutant at different air quality regimes, a K-mean cluster technique has been applied. Five and four optimal cluster numbers have been obtained for the daily patterns of ozone and SO2 respectively. In addition, we studied the daily variation of the temperature, relative and specific humidity and wind speed associated with each air pollutant daily pattern. Ozone daily patterns showed typical daily variations with one exception of a cluster which presents a peak in the early morning. For SO2, the first two clusters present a low mixing ratio, however cluster 3 and 4 are less frequent but with higher levels. The more frequent air pollutant daily patterns do not exceed the threshold defined in the Directive. Nevertheless, clusters with lower frequency (representing between 5 and 7% of days) exceed the thresholds and could be considered as air pollution events.