A simple and precise methodology to determine particulate matter mass in atmospheric filters; validation and application cases.

In the past decades, particulate matter (PM) measurements have been used extensively in atmospheric sciences, as it allows studying the evolution of tracers for different atmospheric processes and the effects of atmospheric pollution on human health. However, measuring PM mass requires a constant control of the laboratory conditions due to its capacity to absorb humidity. For this reason, this study was focused on developing a novel, simple and precise methodology to determine the corrections of the filter mass due to humidity changes. The control and corrections are possible using a "control filter", which is always adapted to the environmental conditions of the laboratory. To check the consistency of this method, it was proved that the mass of any problem filter and that of the control filter behave in a very similar way. This allows quantifying the mass changes of any problem filter by using the control filter, where the problem filters and the control filter must have the same chemical composition and dimensions. To validate this methodology, a comparison was made between the methodology proposed in this study (Method-1) and the one proposed by the EPA (Method-2), which is generally applied. The particulate matter mass (m) was obtained for a problem filter for different weights, achieving similar values using both methods. However, Method-1 still provided reliable mass measurements for relative humidities very different from 50%, even as low as 18%. It was also proved that the adsorption or loss of water by the particulate matter can be neglected, since m is much smaller than the blank filter mass. Method-1 was also employed in several samplings carried out using three PM10 samplers to determine contaminants, such as 7Be and 210Pb, obtaining a good agreement between all particulate masses and activities measured by the three samplers for all samplings.

Evolution of NO2 levels in Spain from 1996 to 2012.

We report on the evolution of tropospheric nitrogen dioxide (NO2) over Spain, focusing on the densely populated cities of Barcelona, Bilbao, Madrid, Sevilla and Valencia, during 17 years, from 1996 to 2012. This data series combines observations from in-situ air quality monitoring networks and the satellite-based instruments GOME and SCIAMACHY. The results in these five cities show a smooth decrease in the NO2 concentrations of ~2% per year in the period 1996-2008, due to the implementation of emissions control environmental legislation, and a more abrupt descend of ~7% per year from 2008 to 2012 as a consequence of the economic recession. In the whole Spanish territory the NO2 levels have decreased by ~22% from 1996 to 2012. Statistical analysis of several economic indicators is used to investigate the different factors driving the NO2 concentration trends over Spain during the last two decades.

A preliminary study on ambient levels of carbonyls, benzene, toluene and xylene in the south-west of the Iberian Peninsula (Huelva coast), Spain.

We report the first observations of volatile organic compound (VOC) concentrations, including aldehydes, in the coastal, industrial area of Huelva near the Doñana National Park (south-west of the Iberian Peninsula). The periods studied were July-September 2008 and February-November 2009. Formaldehyde, acetaldehyde, acetone, propanal, benzene, toluene and m/p-xylenes were identified and quantified. Acetone and formaldehyde were the most abundant carbonyls, followed by acetaldehyde and propanal. Maximum and minimum values for all these compounds in the period of measurement, and their relationship with meteorological parameters or influence of anthropogenic or biogenic emissions, are analysed. Finally, different concentration ratios and correlations were calculated to assess the effect of the anthropogenic or biogenic processes on the observed VOC levels.

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO 2) in a coastal rural area in the southwest of Iberian Peninsula.

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX = NO2 + O3), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station "El Arenosillo" was used. The observed daily cycles of NO x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO x -independent 'regional' contribution (i.e. the O3 background), and a linearly NO x -dependent 'local' contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO2 increases with the increase in NO x concentration during the day. The higher proportion of NO2 observed at night must be due to the conversion of NO to NO2 by the NO + O3 reaction. With regards to the source of the local NO x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO + O2 = 2NO2, at high-NO x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO2, J NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula.

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX = O(3) + NO(2)), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO(2) and OX cycles. The variation of OX concentrations with NO(x) is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO(x)-independent 'regional' contribution (i.e. the O(3) background), and a linearly NO(x)-dependent 'local' contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO(x) was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO(2)]/[OX] and [NO(2)]/[NO(x)] vs. [NO(x)] were analysed to find the fraction of OX in the form of NO(2), and the possible source of the local NO(x)-dependent contribution, respectively. The progressive increase of the ratio [NO(2)]/[OX] with [NO(x)] observed shows a greater proportion of OX in the form of NO(2) as the level of NO( x ) increases. The higher measured values in the ratio [NO(2)]/[NO(x)] should not be attributed to NO(x) emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO(2) photolysis, J (NO(2)) = 0.18-0.64 min(-1), a key atmospheric reaction that influence O(3) production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.

Surface ozone comparison conducted in two rural areas in central-southern Spain.

PURPOSE: The purpose of this work is to contribute to the understanding of the photochemical air pollution analysing the levels and temporal variations of surface ozone in two rural areas situated in central-southern Spain. METHOD: The study is based on ozone hourly data recorded during the overall period between January 2008 and November 2009. The seasonal and daily ozone cycles as well as the number of exceedances of the threshold established in the European Ozone Directive have been calculated and analysed. RESULTS: This study presents the first ozone data registered at these two rural sites in the Iberian Peninsula plateau. Ozone shows a clear seasonal variation with the lowest values in January and November. High ozone concentrations are interrelated with high radiation intensities, temperature and wind directions. The information threshold defined in the European Ozone Directives was exceeded six times, while the limit for protection of human health was exceeded more than 40 times. The limits to protect the vegetation were also exceeded. CONCLUSIONS: Porzuna (near Cabañeros National Park) presents higher ozone levels than Argamasilla during the night-time and during the daytime of the summer months. Ozone levels are lower in Argamasilla probably due to fresh emissions from the close industrial area of Puertollano. The ozone exceedances of the limits defined in the Ozone Directive point out an ozone problem in this rural region.

Synoptic and meteorological characterisation of olive pollen transport in Córdoba province (south-western Spain).

The main goal of the present study was to provide a detailed analysis of olive pollen transport dynamics in the province of Córdoba (south-western Spain) by applying back-trajectory analysis. Pollen data from 2006 and 2007 were analysed at four monitoring sites: Córdoba city in the centre of the province, Baena and Priego de Córdoba located in the south, and El Cabril reserve (Hornachuelos Natural Park) in the north. Particular attention was paid to nine episodes of high pollen counts. Synoptic surface maps were used, and kinematic back-trajectories (3D) were computed using the hybrid single particle Lagrangian integrated trajectory model (HYSPLIT) at 500 m above ground level, run with a time-step of 6 h over a period of 36 h. Findings were analysed in conjunction with daily and bi-hourly airborne pollen data, field phenological data and hourly surface meteorological data recorded at nearby stations: temperature, relative humidity, rainfall, wind direction and wind speed. The results identified two pollen source areas over the Córdoba province, the largest one located in the south, affecting Baena, Priego de Córdoba and Córdoba city, and one smaller located in the west, which determines mainly the pollen cycle over the north of the province, El Cabril. In addition, two air mass circulations were found, one coming from the south and crossing the main olive pollen sources very close to the surface and being frequently associated with higher pollen counts, and the other coming from the west and, in the episodes investigated, influencing mainly the north of the province.