CEAM’s Air Pollution Programme has traditionally worked in three distinct research areas: Atmospheric Chemistry, Pollutant Dynamics (R & D), and Pollutant Dynamics (application).

In recent years, three additional areas – Meteorological Modelling, Photochemical Modelling and Technological Development - have also gained impetus within the programme. They are currently considered “emerging groups” and are expected to attain the status of research areas in the near future.

Listed below are the research activities developed during the year 2008.

I.- ATMOSPHERIC CHEMISTRY AREA

In recent years, practically every country in Europe has had to deal with the problem of photochemical smog on warm and sunny summer days. Many of these countries have also registered high levels of vegetation damage, due in part to elevated concentrations of photo-oxidants, especially ozone.

The various compounds emitted into the atmosphere have repercussions on air quality, human health, changes in agricultural production, effects in vegetation and degradation of materials, etc. The result of all these effects is a higher health expenditure, a significant negative impact on the quality of life, Climate Change and all its implications, etc.

Because of the importance of these effects there has been a steadily growing interest in studying chemical transformations in the atmosphere. This is reflected in the numerous research programmes that have been financed in the last decades in this field. Even so, it is generally accepted that the level of knowledge necessary to develop efficient control strategies for the different conditions currently prevailing in Europe, is still insufficient. And as the chemical mechanisms are not entirely understood, there is not yet a solid enough scientific base to be able to reliably predict the formation of photo-oxidants.

In this respect, EUPHORE constitutes one of the largest and best equipped research installations in Europe for studying atmospheric processes. Its aim was and is to provide atmospheric scientists in Europe and the rest of the world with a platform for dealing with environmental problems related to the chemistry of pollutant formation in the troposphere.

Fig. 1.- EUPHORE atmospheric simulators.

Thanks to photochemical simulators like EUPHORE, reactions that occur in complex systems such as the atmosphere can be investigated directly, through the study of simplified systems that provide detailed kinetic data. The goal is to use these data to better understand the processes taking place in the atmosphere and be able to model them.

Traditional laboratory research activities in the field of atmospheric chemistry present a series of limitations derived from their use of small reactors and artificial light, and resulting in unrealistic working conditions. In contrast, EUPHORE shows important advantages with respect to both laboratory experiments and other simulation chambers:

1. Conditions similar to reality are guaranteed by the large volume of the simulators (200 m3 each ).
2. The simulators are irradiated with solar light.

Moreover, the fact that several international institutions collaborate in the use of these simulation chambers makes the EUPHORE installation a centre of reference for atmospheric chemistry in Europe and favours the interchanges of knowledge among the scientists involved.

In these years, EUPHORE has been used for many scientific research projects. It maintains a strong interaction with the European Union (through the various Framework Programmes), with national organisms (through projects included in the Plan Nacional and/or regionally generated within the Generalitat Valenciana), and with industry.

The Atmospheric Pollution Programme has three main lines:

• Chemical transformations in the troposphere

• Utilization of the EUPHORE atmospheric simulators

• Scientific divulgation and instrument improvement

Chemical transformations in the troposphere..

Objective/Definition To study the chemical transformations of the compounds emitted into the atmosphere and their environmental impact in the troposphere.

 

We are studying the oxidation and photo-oxidation processes of different compounds that affect air quality to a greater or lesser degree (e.g., by increasing tropospheric ozone levels). Evaluation of the impact of compounds like pesticides, aromatic hydrocarbons and aerosols on the oxidation capacity of an atmosphere subjected to the influence of anthropogenic emissions is highly important for designing air pollution control strategies.

Fig. 2.- Emissions to the atmosphere

Another activity developed at EUPHORE is the validation of instrumentation and methods for the analysis of chemical species, including precursors, reaction intermediates and reaction products, for their subsequent use in field measurement campaigns and in modelling reactive chemical systems in the atmosphere.

On the basis of these criteria, the main work in this area in recent years is as follows:

• The EUPHORE group has consolidated a new research line (initiated in 2006 as an internal line) which studies the atmospheric behaviour of certain pesticides. This is the result of obtaining 3 projects (DEPESVAL, ECOPEST and AFIP) financed by the Generalitat Valenciana, the Ministry of Education and Science and the European Union within Interreg IIIC, respectively.

• Other chemical transformation studies carried out in the EUPHORE simulation chambers have dealt with the atmospheric degradation of nitrogenated compounds, especially nitrophenols, and their environmental impact in the troposphere. These compounds are the main products of the oxidation of aromatic hydrocarbons like benzene and toluene. Our studies have primarily focussed on monitoring nitrogen oxides and particulate material, both of which harm human health and cause serious damage to vegetation. For this we used the EUPHORE atmospheric simulators to study the reactions of said compounds with solar light as well as with other oxidizing agents such as ozone and nitrogen oxides.

• As a joint activity (JRA2-WP3) within EUROCHAMP, our group is currently co-leading an intercomparison of aerosol models, together with Dr. Jens Hjorth of the European Union’s Institute for Environment and Sustainability (IES) (Joint Research Centre, ISPRA).

The proposed exercise involves the simulation of experimental data on Secondary Organic Aerosol (SOA) formation obtained in different chambers to estimate the uncertainties in the SOA prediction models and to obtain a basis for analysing the differences between the different models. The basic idea is that the differences are not just in the models, but also in the simulation chambers, with their different designs, operational and measurement infrastructures. This kind of activity can provide useful information: (a) for model validation and (b) on artefacts in the different simulation chambers and their effects on the modelling exercise.

Notable results. 

a) Atmospheric behaviour of pesticides

Within the projects DEPESVAL and ECOPEST, in 2008 we continued the experiments to determine the reaction rate constants for photolysis, OH radicals, and ozone, as well as the experiments aimed at determining the possible reaction products of several pesticides. Most of the data obtained from these experiments is currently being treated and evaluated. Nevertheless, we have been able to determine experimentally both the ozone and the OH radical reaction rate constants for the pesticides hymexazol and chlorpyrifos-methyl. Moreover, the reaction mechanism of the latter pesticide is now being elucidated on the basis of the products determined in the experiments carried out both in the particle and the gas phases.

Most of the pesticides analysed were found to form secondary aerosols. Figure 3 shows examples of hymexazol and chlorpyrifos-methyl aerosol formation in photo-oxidation reactions with OH radicals.

Fig. 3.- . Formation of aerosols in hymexazol and chlorpyrifos-methyl
photo-oxidation experiments under different NOx conditions.

On the other hand, one of the main aims of the PEPEVAL, DEPESVAL and ECOPEST projects, financed by the regional Valencia government’s Health Department, the Generalitat Valenciana and the Ministry of Science and Innovation, respectively, is to carry out field samplings – both in gas phase and in particle phase - in different periods of the year to determine the persistence of these pesticides in the air. For this, samplings were made during 2008 at different times of the year (immediately after pesticide application and, thereafter, at various times) to determine the possible persistence of these pesticides in the air. The areas initially selected for the samplings were Benicarló (Castellón) and Benifaió (Valencia), for their intensive cultivations of citrus fruits and vegetables, respectively, along with 2 control areas in Villar del Arzobispo and Morella. A total of 16 samplings were carried out in Benicarló and Benifaió (La Peira) and 8 were made in the other 2 locations. The data obtained is under evaluation at present.

b) Study of the degradation of nitrophenols

 From the series of experiments performed in the two simulation chambers in 2008 we obtained significant results with respect to the formation of both ozone and particles for the photolysis and photo-oxidation of 2-nitrophenol under different oxidant conditions. The study of these species allows us to verify the influence of the precursor 2-nitrophenol in photochemical smog. Figure 4 shows the formation and degradation profiles of the above-mentioned species.

Fig. 4.- . Profiles of particulate material formation under different
 photo-oxidation conditions (NOx and OH radicals)

The results obtained confirm the influence of organic nitrogenated compounds in the formation of particulate material, thus contributing to the photochemical smog phenomenon.

c)   Intercomparison of aerosols

In relation to this point, the following activities have been carried out:

Operation of the EUPHORE atmospheric simulators.

Objective/Definition The EUPHORE atmospheric simulators are a specially designed installation for the study of chemical processes in atmospheric conditions. These chambers permit studies to be carried out under conditions that simulate reality. They are highly versatile in terms of the class of compound and mixture to be studied and the type of experiment to be performed.

Since its operational launch, one of the aims of this installation has been to provide a platform for Atmospheric Chemistry groups from different European and even North American countries to carry out their research projects. The CEAM Foundation Atmospheric Chemistry group advises them on the technical use of the installation, the design of the experiments and the interpretation of the results. It is also in charge of the analytical instrumentation, the sampling and, in most cases, the data processing.

Notable results

In 2008, the following measurement campaigns were carried out in the EUPHORE simulation chambers by external groups:

a)   The ozonolysis of alkenes was studied in the TRAPOZ (Total Radical Production and Degradation Products from Alkene Ozonolysis) campaign, which lasted 4 weeks from April to May, 2008, and was led by Dr. William Bloss from the University of Birmingham in collaboration with groups from the Universities of Leeds and Leicester, in addition to CEAM.

Alkenes are emitted by the petrochemical industry. Some also originate from biogenic emissions. The aim was to determine the production of OH radicals from alkenes exposed to solar radiation in the presence of ozone and study the effect of humidity in the generation of said radicals. The compounds studied were ethane, trans-2-butene, isobutene, isoprene, limonene, myrcene, a-cedrene and a-pinene, under different humidity conditions, carbon monoxide concentration and/or cyclohexane concentration in the atmospheric simulator.

The monitoring of the compounds and organic products generated during these reactions helped in the investigation into both the production of radicals and the chemical mechanisms involved in this kind of reaction. In addition, the results obtained have been used to adjust the predictions made by MCM, a photochemical model developed at the University of Birmingh

b)   Study of the atmospheric degradation of amines within the project Atmospheric Degradation of Amines (ADA), led by Professor Claus J. Nielson, University of Oslo. In September 2008, a 3-week measurement campaign was conducted to study methylamine, dimethylamine, trimethylamine, both normal and deuterated. Several photolysis experiments were performed with different initial concentrations of NOx by using nitrous acid as well as hydrogen peroxide. These experiments were aimed as much at determining the reaction products as they were at studying the relative kinetics between the normal and deuterated compounds, since recent studies have revealed that the photochemical degradation of these compounds has negative effects on the environment. In these experiments the composition of both the gaseous phase and the aerosols formed was analysed.

c)   Study of the atmospheric degradation of unsaturated oxygenated compounds within the project Atmospheric Oxidation Reactions of Unsaturated Oxygenated Compounds, led by Dr. Howard Sidebottom, University College, Dublin, and financed by The Science Foundation Ireland – “New Frontiers.” This involved a 2-week measurement campaign, at the end of May, beginning of June, 2008. The compounds studied were: acrylic acid, vinyl acetate, 6-methyl-5-hepten-2-ol, methyl acrylate, and trifluoropropene in different conditions. In addition to the reactions with ozone, photooxidation reactions were also carried out with HONO and with hydrogen peroxide. The aim of these experiments was to determine both the chemical and the physical parameters, e.g., the reaction constant, and to identify the products in order to elucidate details of the reaction mechanisms. For this, both the gas and the particulate (aerosols formed during the reactions) phases were analysed.

d)   During 2008, a group from CIEMAT supervised by Dr. M. García Vivanco carried out a measurement campaign to check AOS models against experimental data from the simulation chambers. For this, they used the simulation chambers to perform 8 experiments on the photochemical degradation of anthropogenic hydrocarbons and aerosol formation. These experiments focused on the study of:

The aim was to evaluate the capacity of the models to simulate the formation of particle-phase products and their partitioning between the gas and the solid phases.

Scientific divulgation and instrument improvements

 

Objective/Definition To improve our understanding of atmospheric chemistry an interchange of information with other relevant Institutions is absolutely necessary. In this sense, within the project EUROCHAMP, EUPHORE has coordinated the development of a database which gathers information on experiments carried out in atmospheric simulation chambers and makes it accessible to members and, in extension, to the scientific community as a whole.

This project integrates Europe’s most important environmental reaction chambers for the study of atmospheric chemical processes into a European-scale infrastructure. The consortium members provide their experience and knowledge in atmospheric chemistry to multidisciplinary researchers responsible for defining future directives and laws, and offer an infrastructure which can be used by interested parties to solve a wide range of problems related to atmospheric science.

 

The main aims of the EUROCHAMP project are:

• To adopt a series of initiatives aimed at achieving effective multidisciplinary cooperation between atmospheric scientists and scientists from other closely related disciplines, through the project’s three interrelated activities.

• To improve and optimize the efficiency of the infrastructures involved in the project. For this, 2 interrelated research activities have been defined in the EUROCHAMP work programme: development and refinement of analytical equipment and development of chemical modelling techniques.

• Within the two combined research activities, significant progress has been made towards designing and developing new instrumentation and developing chemical models.

To cover these aspects, the database - operative since 2005 – contains information on intercomparison of instruments, chemistry in gaseous phase, and aerosol studies.

In addition to the improvements developed within the framework of the EUROCHAMP project, EUPHORE is also carrying out ongoing research activities aimed at improving current instrumentation and current sampling and analysis methods.

Lastly, a workshop has been organized to prepare an instrument intercomparison campaign for measuring HONO, a very important compound in the atmospheric formation of OH radicals which trigger the photochemical processes.

Notable results

The public presence of EUPHORE on Internet has been established through  http://euphore.es/.

Fig. 5.- . Initial page of the EUPHORE web site (http://euphore.es).

This has brought with it the necessity of making a rigourous categorization of the objects published and their access privileges, and of implementing the methods for setting up these privilege policies. In this sense the user policy implemented for the EUPHORE web follows the P3P Platform for Privacy Preferences model proposed by the W3 Consortium.

The organization of the database is shown in the following figure.

Fig. 6.- . Diagram of EUPHORE web site

a)    Up to the year 2008, 480 datasets from 13 institutes had been incorporated          into the EUROCHAMP database (http://eurochamp-database.es/) using a unified format. This database has continued to show significant growth as it incorporates new elements aimed at making it a solid platform to carry out very sought-after services such as intercomparing chambers and instruments, and developing and evaluating chemical models of atmospheric processes.

During the year 2008, besides defining rules to ensure the quality and analysis of pure data, we have continued improving the database. This is seen in the following: We have continued our efforts to facilitate the management of the data bases. We have added tools to control the quality of the data incorporated by the institutions. We have also worked to facilitate data maintenance and data searches on the part of the different institutes by keeping an open line of communication with them and taking into account their opinions as final users (user-driven design). Lastly, we have also improved the generation of use reports.

b)      We have continued our work on developing and improving software for analysing data obtained with spectroscopic techniques, especially DOAS (ultra-violet) and FTIR (infrared), with the aim of optimizing the analysis process for obtaining pollutant measurements. The application of this software to the analysis of data from projects in which EUPHORE collaborates has yielded very satisfactory results. We have continued automating most of the analytical process with the result to date of reducing the user intervention and thus also the error associated with the subjectivity of non-automatic analyses.

c)      Work in the solid-phase microextraction sampling technique has also continued during 2008. It has been applied to the determination of carbonyls in several relevant atmospheric systems: mixtures of aromatic biogenic precursors, ozonolysis of alkenes, and atmospheric degradation of amines, among others. Characterization studies of active sampling systems has also continued with the aim of improving their sensitivity and as a preliminary step towards automating the methodology and applying it in field measurements..

d)      To model the experiments performed in the EUPHORE simulators a graphic interface based on the one developed by Chris Martin (University of Leeds) has been developed at CEAM with a few changes. This model is developed in Fortran, uses the MCM as the chemical mechanism, and is structured in different configuration archives and programs. The interface is programmed in C, including the GTK+ libraries. Use of this interface permits an easy configuration of model parameters making it unnecessary for the user to directly access his/her code and thereby generate modifications that cause the model to operate incorrectly. Moreover, this interface enables model results to be visualized in both table and graph form. With this work, M. Vázquez (CEAM Foundation) has obtained the Diploma of Advanced Studies (DEA) from the University of Valencia Chemical Engineering doctorate programme.

e)      Within the framework of the ESF-INTROP programme, we organized the FIONA (Formal Intercomparisons of Observations of Nitrous Acid) technical workshop at EUPHORE on 17-18 November 2008; 23 representatives from 12 research institutions and centres in France, Germany, Ireland, USA, Czech Republic and Spain participated. ¡

The aim of the workshop was the scientific and technical organization of a HONO measurement campaign to be held at EUPHORE from 11 to 29 May 2009. Twenty groups from nine countries are expected to participate in this campaign, which will allow them to intercompare a wide range of measuring instruments while performing experiments that simulate urban and semi-rural conditions. Emphasis will be placed not only on the chemistry but also on possible interferences from the measuring methods used. Because of the large number of groups and instruments involved, the workshop dealt with themes such as overall coordination, logistics, plan for the experiments, etc.

Information relative to this workshop can be found on the EUROCHAMP web page: http//www.eurochamp.org/events/2008/fiona_techn_ws.

 

Other activities

Objective/Definition A priority objective of the EUPHORE group is scientific interaction with other relevant institutions to share knowledge and collaborate in joint projects. Thus, in addition to the work developed in the simulation chambers the EUPHORE group also carries out field measurement activities and has organized a workshop to prepare an instrument intercomparison campaign for 2010. In this way, the existing infrastructure is made highly versatile and profitable.

Notable results.

1. Identification of compounds emitted in gas phase (BTXE, linear hydrocarbons, aldehydes and ketones) and in particle phase (PM10 PAHs and carboxylic acids) in an industrial complex in Puertollano (Ciudad Real) and study of the influence of these emissions in tropospheric ozone formation. Estimation of the levels of compounds of interest in typical scenarios, e.g., days with established breeze regimes.
   These measurements have been focussed on establishing (according to current knowledge on photochemical processes) a relation between the ozone values obtained and the levels of other species. The following figure shows the correlation found:

Fig. 7.- . Correlation between ozone levels and BTXE,
with carboxylic acids as degradation products.

2. With the objective of interchanging current knowledge, one of our researchers, Amalia Muñoz, completed her stay at the University College Cork (UCC, Ireland) Atmospheric Chemistry Department in 2008, financed by the Spanish Ministry of Education and Science in the framework of the “José Castillejo” aid programme for young Spanish Phds to spend a period of time in foreign research centres. One of the activities she carried out there was to use the UCC atmospheric simulator to study how different scavengers affect secondary aerosol formation. Some of the techniques utilized there will be implanted in EUPHORE in the near future. Dr. Muñoz, as an invited professor, also gave classes in Atmospheric Chemistry and Instrument Analysis to advanced students.

 

3. The CEAM Foundation also collaborates with several organisms and programmes. During 2008, and up to the present, two second-cycle FP students have been carrying out their practice training at EUPHORE under the supervision of two of our researchers. In addition, an ERASMUS student from the University of Leeds (United Kingdom) is finishing her degree project at EUPHORE under the auspices of the ADEIT  programme. Her project has been centred on developing the essential components for automating the solid-phase microextraction technique, specifically the characterization of active sampling systems, with the aim of improving their efficiency.

d)    One of our group’s researchers, Elena Alvarez, successfully defended her doctoral thesis, entitled “Development and implementation of a SPME-based methodology for sampling and quantifying reaction intermediates generated during the course of gas-phase reactions in the EUPHORE photochemical reactors,” at the Department of Analytical Chemistry, University of Cordoba, on November 11, 2008. The objective of this thesis, directed by Professors Valcarcel and Hjorth of said department, was to confirm the formation of key dicarbonylic intermediates in the photooxidation of aromatics. This determination is complicated by the great photochemical reactivity of these compounds. The most relevant result of this doctoral thesis has been the semi-quantitative estimation of the formation of these compounds in gas phases, which is of key importance in helping to determine the mechanisms that describe the atmospheric degradation of aromatic compounds.

e)     Within the European Science Foundation programme INTROP (Interdisciplinary Tropospheric Research: from the laboratory to global change), CEAM’s M.Vázquez spent two weeks at the University of Leeds (United Kingdom) working on her doctoral thesis directed by Professor Michael J. Pilling in collaboration with Professors C. Martin and A. Rickard (all at U. of Leeds).  This work involves modelling the degradation of volatile organic compounds in simulation chambers on the basis of the Master Chemical Mechanism, for subsequent application in experimental field campaigns.

f)      Also within the INTROP programme, CEAM’s E. Borrás spent two weeks at the University of Wuppertal (Germany) as part of her doctoral thesis directed by Prof. Ian Barnes (U. of Wuppertal). This thesis studies the photochemical degradation of nitroaromatic compounds like nitrophenols and its effect in the formation of ozone and, especially, of particulate material, for subsequent application in photochemical modelling.

g)     And, lastly, within the INTROP programme, CEAM’s M. Ródenas was at LISA-CNRS (Paris) from 20 January – 2 March 2008, working on her doctoral thesis with the group led by Dr. Jean-François Doussin. Her thesis is related to the development of spectroscopic data analysis software for measuring pollutants. As a result of this work, CEAM software has been improved to extend its application to a larger number of samples. Moreover, an intercomparison of LISA and CEAM software was carried out using real samples, and CEAM software was found to be able to eliminate interferences from unknown compounds, thus improving the quality of the data. In addition, it was agreed that the project EUROCHAMP-II would incorporate a part on spectroscopic data bases and analysis methods, which would include the work carried out during M. Ródenas’ stay at LISA.

 

II.- Pollutant Dynamics Area - R & D

This has included work in two aspects 

 

Atmospheric dispersion of pollutants.

Objective/Definition The general aim of this line is to characterize the meso-meteorological processes responsible for the transport and dispersion of air pollutants through the use of field measurements, meteorology and air quality network data, and numerical modelling (meso-meteorological and atmospheric dispersion) tools.

The main research activities developed within this line can be grouped into three thematic blocks: (a) the description of the physical processes that drive air pollution in the Mediterranean context, (b) the characterization of the synergies and interactions between the different meteorological scales, and (c) the adaptation and integrated use of methodologies for the regionalization and application of air quality/air pollution dispersion models for the Mediterranean environment.

Worthy of note is the interdisciplinary nature of some of the activities developed in this line, which may involve collaborations with other lines and research areas within and outside of the Air Pollution Programme.

Notable Results

a)Within the project “State of air quality in the northern counties of the Valencia Autonomy” we have continued our analysis of the available database (Figures 8 and 9).

Fig. 8.Proportion of records that exceed the 130 ug/m3 threshold level in the different
characteristic sections around the Andorra power plantt

Fig. 9. Proportion of records that exceed the 100 ug/m3 threshold level
along the section that joins the Torre Miró mountain pass with Castellfort

b) In the context of the contract with the Ministry of the Environment on tropospheric ozone in the Iberian Peninsula, CEAM has collaborated both in setting-up and in carrying-out the measurement campaign that took place in Puertollano from 2-13 June 2008.

c) Also in the context of the contract with the Ministry of the Environment on tropospheric ozone in the Iberian Peninsula, CEAM has collaborated by making a preliminary study of the dispersion patterns around Puertollano (Figure 10).

Fig. 10: Profiles of the SO2 measurements taken by the mobile unit, as projected onto the highway network. The blue line represents the SO2 concentration aloft, and the red line represents the surface concentration of SO2.

d) In the context of the European Project CIRCE, “Climate Change and Impact Research: the Mediterranean Environment”, the activities defined for 2008 on: “Atmospheric flow regimes in the Mediterranean Basin” (Figure 11) have been carried out in a satisfactory way.    

Fig. 11: Comparison of time series on wind direction and speed between experimental
measurements and RAMS meso-meteorological model outputs.

e) Also in the context of the European Project CIRCE, our group has collaborated with the CEAM Meteorology group, the University of the Basque Country and the Institute Juan Almera (CSIC) in the project activities planned for the year 2008.

f) During this year, our research collaborator, Francisco Rovira, has begun his doctoral thesis work in the framework of the European project CIRCE.

g) We have continued participating and collaborating in the RETEMCA excellence network, “Modelling air quality in Spain” (CTM2007-30877-E/TECNO), coordinated by CIEMAT (Figure 12).

h)Participation and collaboration in the MEDOC thematic network, “Western Mediterranean Meteorology” (CGL2007-29820-E/CLI.  Renewable: 2008-2010). Within this network we collaborated in organizing the “First Workshop on Western Mediterranean Meteorology and Climatology,” which took place in Barcelona on 28 November 2008.

Fig. 12: Modelling example of point source SO2 emissions impacting on the ground surface

i) Active collaboration on the journal Thetys, “Revista del Temps i el Clima de la Mediterrània Occidental” (http://www.tethys.cat/), as part of its editorial board

j)  Also part of the editorial board of the journal “Air, Soil and Water Research” (http://www.la-press.com/journal.php?journal id=99)

k)  One of our activities in the (2004-2007) National Plan R&D project TRANSREG (Seasonality of the meteorological processes responsible for the regional transport of air pollutants CGL2007-65359/CLI: 1/10/2007-31/09/2010) was to design the project’s website and release it onto Internet as http://www.ceam.es/transreg/. This website has now completed its first year of use

l) Also in the context of the TRANSREG project, we have collaborated with CEAM’s emerging Technological Development group to organize and carry out an intercalibration campaign (for the remote sensing of NO2 and SO2) using 3 COSPECs and a mini-DOAS (on loan from the Technological Institute of Renewable Energy, ITER). This campaign took place in the vicinity of the Andorra power plant from 5-8 May 2008.

Fig. 13.Intercalibration of 3 COSPECs and a mini-DOAS in the vicinity of the Andorra power plant.

m) Also in the context of the TRANSREG project, we have organized and carried out (6-8 October 2008) the measurement campaign programmed for this year in the industrial area of Sagunto Port.

n) Within the project OSIRIS (“Open architecture for smart and interoperable networks in risk management based on in-situ sensors”) in the European Union’s 6th Framework Programme, and the subcontract signed between GMV and CEAM, we installed a real-time continuous NO2 remote measuring system in one of the municipal buses in the city of Valladolid (Figure 14).

Fig.  14: Detail of the COSPEC installed in a Valladolid municipal bus.

o) During 2008, we have continued our participation in COST Action 728, attending its various meetings as Experts and National Delegates.

p) Also within the framework of COST 728, and in collaboration with GURME (“GAW Urban Research Meteorology and Environment Project”) and the World Meteorological Organization (WMO), we have helped to prepare a document entitled “Overview of Tools and Methods for Meteorological and Air Pollution Mesoscale Model Evaluation and User Training”, edited by the WMO (WMO/TD-No 1457).

q) Within the context of the VALENCIA-QUALITY project, we have collaborated with the Pollutant Dynamics (Application) group and the Technological Development emerging group on the design and systematic execution of 2 month-long campaigns around the city of Valencia using a mobile unit equipped with a COSPEC and an NO2 monitor (Figure 15).

Fig. 15: NO2 measurement registered in the city of Valencia.

Air Quality Monitoring Networks

Objective/Definition

Automatic air pollution monitoring networks are the main instrument established by European legislation to evaluate air quality (Directive 2008/50/CE). This evaluation, which consists of checking the degree of compliance with the reference levels defined for a group of air pollutants, is the basis for deriving measures to improve, or conserve, the air quality in a territory. Moreover, the databases in these networks, with time series that start in the mid-1990s for most of Spain’s autonomous communities, are valuable sources of information for pollutant dynamics studies. The knowledge they supply is fundamental in order that successive laws in this field can better provide for the particular pollutant dynamics in the Mediterranean Basin

Consequently, the aim of our work in network data exploitation is twofold: first, to develop a methodology for optimizing the networks as an evaluation tool. With this, public and private managers would have an effective instrument for overseeing air quality within the current legal framework. Second, and complementarily, our aim is to apply the analysis of the network databases to the study of pollutant dynamics in the context of several of the research projects being carried out by CEAM

The main aspects involved in exploiting the network data are: interpretation of the concentration and meteorological data in terms of the factors intervening in their evolution, characterization both of space-time patterns and of episodic situations, quality control of the data, and development of specific software tools for processing and analysing the data (programming)

Notable activities.

I.  Relative to our collaboration with the Valencia General Directorate of Environmental Quality and Climate Change. This collaboration, initiated in 1996, is geared towards providing continuous support for the different activities involved in managing the Valencia Community Air Pollution Monitoring Network (R.V.C.C.A.). There is thus a close cooperation between CEAM scientists, Valencia Regional Government technical personnel, and technicians responsible for network maintenance.

a)     R.V.C.C.A. Quality control/ Data validation for 2008. Preparation of weekly and monthly reports on validation results and incidents detected.

b)    Technical assistance for network optimization (site selection for new or relocated stations, efficiency analysis of measurement equipment, etc.). Preparation of corresponding reports.

c)    Organizing the workshops indicated below in (d).

II. Relative to our contract with the Environment Ministry: “Study and Evaluation of Tropospheric Air Pollution in Spain” (renewed for the period July 2007- July 2009). The aim of this study is to establish a methodology for satisfactorily evaluating Spanish air quality in relation to tropospheric ozone levels. This methodology must conform both to the criteria stipulated in EU Directive 2002/03/CE and to the most up-to-date scientific and technological research results. It will mainly be based in the optimization of evaluation tools and the development of interpretive procedures.

d)    Carrying out the activities planned for the second and third semesters in the contract renewal, and preparation of the corresponding reports, including:

e)    Attendance at the meetings monitoring the contracted activities.

f)     Attendance at the atmosphere working group meetings of the environment sectorial conference.

• In the framework of this group and as a result of a proposal made at the Workshop cited above: A new working group has been set up to prepare a document-guide on air quality network data validation (aimed at Spanish air quality managers).

III.  Relative to our participation in the Ministry of the Environment project CALIOPE (Air Quality Operational System for Spain), in collaboration with BSC-CNS, CSIC and CIEMAT (finalized in June 2008; new proposal for 2008-2010 approved and initiated in July 2008).

The aim of this project is to provide an air quality forecasting system with high spatial resolution for the Iberian Peninsula, Balearic Islands and Canary Islands, and with very high resolution nesting in urban areas. CEAM’s participation is especially concentrated in the final validation of the model, in its operational phase (following a standardized procedure in which the results of the numerical simulations are contrasted with the concentrations registered at a set of representative stations). The most notable activities in 2008 are:

g)    Finalization of the work associated with the Activity “Validation of the air quality forecasting system: measurement collection and analysis vs the forecast”, coordinated by CEAM.

• A high-spatial-resolution characterization of the spatial distribution of ground-level NO2 in the city of Valencia by using passive sensors in different time periods;
• A characterization of port/city exchanges on the basis of systematic measurements taken from a vehicle moving along the interface between these two spaces.

The aim was to find correlations between the traffic (emissions) and the spatial/temporal distribution of the ground-level concentrations, and use these correlations for a future reduction strategy which would probably involve limiting vehicle emissions in the city (by limiting the traffic).

Fig. 22.- City of Valencia sampling network, consisting of 98 sampling points.

Fig. 23.- Location of the 2 study sites near the city of Lorca, and example of the ground-level concentration results obtained (maximum ammonia levels) from the 2 experimental networks set up.

g)  Throughout 2008, we continued developing our experimental activities within the project “Evaluation of the potential odour impact from 2 purine treatment plants located near Lorca.” CEAM’s participation in this project – led by the Segura Edaphology and Applied Biology Centre, which is part of the CSIC network – involved obtaining experimental information on ambient ammonia and hydrogen sulfide concentrations for the dual purpose of:

• Documenting the magnitude of the presence of these species under different environmental conditions with the use of several sampling technologies

• Establishing a possible cause/effect relationship with respect to the problem sources, through an ad hoc strategy and measurement network design.

• The work we carried out consisted of taking 2 kinds of ground-level experimental measurements:

• Spatial campaigns, which involved setting up an H2S and NH3 passive-sensor network in the environs of the potential emission sources,

• Specific campaigns, which involved taking on-site measurements of the ground-level concentrations of both species at different geographic points with respect to the potential emission sources.

IV.- Emergent Group: Technological Development:

 

Objective/Definition:

Optimize, modify and, as a last step, manufacture new instrumentation to cover CEAM research requirements.

The knowledge and experience that CEAM researchers have acquired through the years with respect to air pollution measurements have led to new instrumentation needs which cannot be satisfied by currently available products. For this reason, CEAM created the Technological Development emergent group. This research line is divided into 4 areas: optimization and state-of-the-art updating of the COSPEC V remote sensor of air pollutants (SO2, NO2), development of new instrumentation to increase the range of pollutants that can be measured (BrO, HCl, NH3, particulates, etc.), development of new instrumentation in other fields of interest (vegetation effects, meteorology, etc.), preparation of data acquisition systems that facilitate more exact and efficient data acquisition and interpretation, working out new measurement concepts to help eliminate uncertainties in the results.

Notable results:

Within the TRANSREG project we have carried out the activities associated with the first year of the project. These activities mainly involved deploying the instruments necessary for the experimental campaigns and designing the two mobile units used therein. In addition, software applications were also generated to interpret the data acquired.

An intercalibration campaign (for the remote measurement of NO2 and SO2) was organized and carried out using 3 COSPECs and 1 mini-DOAS (lent by the Canary Island Technological Institute of Renewable Energies, ITER) in the environs of the Andorra power plant from 5-8 May 2008.

Also in the context of the TRANSREG project activities for 2008, we organized and carried out a measurement campaign in the industrial zone of Puerto de Sagunto from 6-8 October 2008.

Within the OSIRIS project we installed a COSPEC in a Valladolid municipal bus. For this, we installed in the GMV system the electromechanical interface designed by CEAM, which allowed the COSPEC to take measurements without the presence of an operator. We also developed a software tool to process the data in real time. During the development of the project there was a migration of software tools to the LINUX operating system. The figure below shows the COSPEC installation in the city bus.

Fig.  24:  Detail of the COSPEC installation in a Valladolid municipal bus.

The first prototype of this system was the result of the in-house development project SENSOR. The electronic and control elements were purchased and assembled, and the initial operating tests of the system were carried out in the laboratory. With this prototype we load-tested the system to estimate its pneumatic requirements. Then we designed a second prototype to rectify the problems encountered in the preliminary design.

Within the MOTAS project we purchased a system for developing this type of technology. The aim of the project is to design an intelligent measurement network using this kind of wireless sensor. The first step has involved the in-house testing of a small network consisting of 2 elements. The technological development group has been trying to adapt these general-use electronic elements to the specific requirements of CEAM. This group has worked especially on adding a small function to the way the microcontroller acquires analog signals.

In the VALENCIA QUALITY project we have developed an experimental set-up of the system design to be used in measurement campaigns around the port of Valencia. Georeferencing software tools have also been developed to graph the results in Google Earth format.

In the context of the Ministry of the Environment contract on tropospheric ozone in the Iberian Peninsula we have carried out a preliminary study of the dispersion patterns in the vicinity of Puertollano.