Gas monitoring methodology and application to CCS projects as defined by atmospheric and remote sensing survey in the natural analogue of Campo de Calatrava

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. Geophysical, ground deformation and geochemical monitoring have been carried out to detect potential leakage, and, in the event that this occurs, identify and quantify it. This monitoring needs to be developed prior, during and after the injection stage. For a correct interpretation and quantification of the leakage, it is essential to establish a pre-injection characterization (baseline) of the area affected by the CO2 storage at reservoir level as well as at shallow depth, surface and atmosphere, via soil gas measurements. Therefore, the methodological approach is important because it can affect the spatial and temporal variability of this flux and even jeopardize the total value of CO2 in a given area. In this sense, measurements of CO2 flux were done using portable infrared analyzers (i.e., accumulation chambers) adapted to monitoring the geological storage of CO2, and other measurements of trace gases, e.g. radon isotopes and remote sensing imagery were tested in the natural analogue of Campo de Calatrava (Ciudad Real, Spain) with the aim to apply in CO2 leakage detection; thus, observing a high correlation between CO2 and radon (r=0,858) and detecting some vegetation indices that may be successfully applied for the leakage detection.

Estrategias de monitorización de CO2 y otros gases en los estudios de análogos naturales

La Universidad Politécnica de Madrid (UPM) y la Università degli Studi di Firenze (UniFi), bajo la coordinación técnica de AMPHOS21, participan desde 2009 en el proyecto de investigación “Estrategias de Monitorización de CO2 y otros gases en el estudio de Análogos Naturales”, financiado por la Fundación Ciudad de la Energía (CIUDEN) en el marco del Proyecto Compostilla OXYCFB300 (http://www.compostillaproject.eu), del Programa “European Energy Program for Recovery - EEPR”. El objetivo principal del proyecto fue el desarrollo y puesta a punto de metodologías de monitorización superficiales para su aplicación en el seguimiento y control de los emplazamientos donde se realice el almacenamiento geológico de CO2, analizando técnicas que permitan detectar y cuantificar las posibles fugas de CO2 a la atmósfera. Los trabajos se realizaron tanto en análogos naturales (españoles e italianos) como en la Planta de Desarrollo Tecnológico de Almacenamiento de CO2 de Hontomín. Las técnicas analizadas se centran en la medición de gases y aguas superficiales (de escorrentía y manantiales). En cuanto a la medición de gases se analizó el flujo de CO2 que emana desde el suelo a la atmósfera y la aplicabilidad de trazadores naturales (como el radón) para la detección e identificación de las fugas de CO2. En cuanto al análisis químico de las aguas se analizaron los datos geoquímicos e isotópicos y los gases disueltos en las aguas de los alrededores de la PDT de Hontomín, con objeto de determinar qué parámetros son los más apropiados para la detección de una posible migración del CO2 inyectado, o de la salmuera, a los ambientes superficiales. Las medidas de flujo de CO2 se realizaron con la técnica de la cámara de acúmulo. A pesar de ser una técnica desarrollada y aplicada en diferentes ámbitos científicos se estimó necesario adaptar un protocolo de medida y de análisis de datos a las características específicas de los proyectos de captura y almacenamiento de CO2 (CAC). Donde los flujos de CO2 esperados son bajos y en caso de producirse una fuga habrá que detectar pequeñas variaciones en los valores flujo con un “ruido” en la señal alto, debido a actividad biológica en el suelo. La medida de flujo de CO2 mediante la técnica de la cámara de acúmulo se puede realizar sin limpiar la superficie donde se coloca la cámara o limpiando y esperando al reequilibrio del flujo después de la distorsión al sistema. Sin embargo, los resultados obtenidos después de limpiar y esperar muestran menor dispersión, lo que nos indica que este procedimiento es el mejor para la monitorización de los complejos de almacenamiento geológico de CO2. El protocolo de medida resultante, utilizado para la obtención de la línea base de flujo de CO2 en Hontomín, sigue los siguiente pasos: a) con una espátula se prepara el punto de medición limpiando y retirando el recubrimiento vegetal o la primera capa compacta de suelo, b) se espera un tiempo para la realización de la medida de flujo, facilitando el reequilibrio del flujo del gas tras la alteración provocada en el suelo y c) se realiza la medida de flujo de CO2. Una vez realizada la medición de flujo de CO2, y detectada si existen zonas de anomalías, se debe estimar la cantidad de CO2 que se está escapando a la atmósfera (emanación total), con el objetivo de cuantificar la posible fuga. Existen un amplio rango de metodologías para realizar dicha estimación, siendo necesario entender cuáles son las más apropiadas para obtener el valor más representativo del sistema. En esta tesis se comparan seis técnicas estadísticas: media aritmética, estimador insegado de la media (aplicando la función de Sichel), remuestreo con reemplazamiento (bootstrap), separación en diferentes poblaciones mediante métodos gráficos y métodos basados en criterios de máxima verosimilitud, y la simulación Gaussiana secuencial. Para este análisis se realizaron ocho campañas de muestreo, tanto en la Planta de Desarrollo Tecnológico de Hontomón como en análogos naturales (italianos y españoles). Los resultados muestran que la simulación Gaussiana secuencial suele ser el método más preciso para realizar el cálculo, sin embargo, existen ocasiones donde otros métodos son más apropiados. Como consecuencia, se desarrolla un procedimiento de actuación para seleccionar el método que proporcione el mejor estimador. Este procedimiento consiste, en primer lugar, en realizar un análisis variográfico. Si existe una autocorrelación entre los datos, modelizada mediante el variograma, la mejor técnica para calcular la emanación total y su intervalo de confianza es la simulación Gaussiana secuencial (sGs). Si los datos son independientes se debe comprobar la distribución muestral, aplicando la media aritmética o el estimador insesgado de la media (Sichel) para datos normales o lognormales respectivamente. Cuando los datos no son normales o corresponden a una mezcla de poblaciones la mejor técnica de estimación es la de remuestreo con reemplazamiento (bootstrap). Siguiendo este procedimiento el máximo valor del intervalo de confianza estuvo en el orden del ±20/25%, con la mayoría de valores comprendidos entre ±3,5% y ±8%. La identificación de las diferentes poblaciones muestrales en los datos de flujo de CO2 puede ayudar a interpretar los resultados obtenidos, toda vez que esta distribución se ve afectada por la presencia de varios procesos geoquímicos como, por ejemplo, una fuente geológica o biológica del CO2. Así pues, este análisis puede ser una herramienta útil en el programa de monitorización, donde el principal objetivo es demostrar que no hay fugas desde el reservorio a la atmósfera y, si ocurren, detectarlas y cuantificarlas. Los resultados obtenidos muestran que el mejor proceso para realizar la separación de poblaciones está basado en criterios de máxima verosimilitud. Los procedimientos gráficos, aunque existen pautas para realizarlos, tienen un cierto grado de subjetividad en la interpretación de manera que los resultados son menos reproducibles. Durante el desarrollo de la tesis se analizó, en análogos naturales, la relación existente entre el CO2 y los isótopos del radón (222Rn y 220Rn), detectándose en todas las zonas de emisión de CO2 una relación positiva entre los valores de concentración de 222Rn en aire del suelo y el flujo de CO2. Comparando la concentración de 220Rn con el flujo de CO2 la relación no es tan clara, mientras que en algunos casos aumenta en otros se detecta una disminución, hecho que parece estar relacionado con la profundidad de origen del radón. Estos resultados confirmarían la posible aplicación de los isótopos del radón como trazadores del origen de los gases y su aplicación en la detección de fugas. Con respecto a la determinación de la línea base de flujo CO2 en la PDT de Hontomín, se realizaron mediciones con la cámara de acúmulo en las proximidades de los sondeos petrolíferos, perforados en los ochenta y denominados H-1, H-2, H-3 y H-4, en la zona donde se instalarán el sondeo de inyección (H-I) y el de monitorización (H-A) y en las proximidades de la falla sur. Desde noviembre de 2009 a abril de 2011 se realizaron siete campañas de muestreo, adquiriéndose más de 4.000 registros de flujo de CO2 con los que se determinó la línea base y su variación estacional. Los valores obtenidos fueron bajos (valores medios entre 5 y 13 g•m-2•d-1), detectándose pocos valores anómalos, principalmente en las proximidades del sondeo H-2. Sin embargo, estos valores no se pudieron asociar a una fuente profunda del CO2 y seguramente estuvieran más relacionados con procesos biológicos, como la respiración del suelo. No se detectaron valores anómalos cerca del sistema de fracturación (falla Ubierna), toda vez que en esta zona los valores de flujo son tan bajos como en el resto de puntos de muestreo. En este sentido, los valores de flujo de CO2 aparentemente están controlados por la actividad biológica, corroborado al obtenerse los menores valores durante los meses de otoño-invierno e ir aumentando en los periodos cálidos. Se calcularon dos grupos de valores de referencia, el primer grupo (UCL50) es 5 g•m-2•d-1 en las zonas no aradas en los meses de otoño-invierno y 3,5 y 12 g•m-2•d-1 en primavera-verano para zonas aradas y no aradas, respectivamente. El segundo grupo (UCL99) corresponde a 26 g•m-2•d- 1 durante los meses de otoño-invierno en las zonas no aradas y 34 y 42 g•m-2•d-1 para los meses de primavera-verano en zonas aradas y no aradas, respectivamente. Flujos mayores a estos valores de referencia podrían ser indicativos de una posible fuga durante la inyección y posterior a la misma. Los primeros datos geoquímicos e isotópicos de las aguas superficiales (de escorrentía y de manantiales) en el área de Hontomín–Huermeces fueron analizados. Los datos sugieren que las aguas estudiadas están relacionadas con aguas meteóricas con un circuito hidrogeológico superficial, caracterizadas por valores de TDS relativamente bajos (menor a 800 mg/L) y una fácie hidrogeoquímica de Ca2+(Mg2+)-HCO3 −. Algunas aguas de manantiales se caracterizan por concentraciones elevadas de NO3 − (concentraciones de hasta 123 mg/l), lo que sugiere una contaminación antropogénica. Se obtuvieron concentraciones anómalas de of Cl−, SO4 2−, As, B y Ba en dos manantiales cercanos a los sondeos petrolíferos y en el rio Ubierna, estos componentes son probablemente indicadores de una posible mezcla entre los acuíferos profundos y superficiales. El estudio de los gases disueltos en las aguas también evidencia el circuito superficial de las aguas. Estando, por lo general, dominado por la componente atmosférica (N2, O2 y Ar). Sin embargo, en algunos casos el gas predominante fue el CO2 (con concentraciones que llegan al 63% v/v), aunque los valores isotópicos del carbono (<-17,7 ‰) muestran que lo más probable es que esté relacionado con un origen biológico. Los datos geoquímicos e isotópicos de las aguas superficiales obtenidos en la zona de Hontomín se pueden considerar como el valor de fondo con el que comparar durante la fase operacional, la clausura y posterior a la clausura. En este sentido, la composición de los elementos mayoritarios y traza, la composición isotópica del carbono del CO2 disuelto y del TDIC (Carbono inorgánico disuelto) y algunos elementos traza se pueden considerar como parámetros adecuados para detectar la migración del CO2 a los ambientes superficiales. ABSTRACT Since 2009, a group made up of Universidad Politécnica de Madrid (UPM; Spain) and Università degli Studi Firenze (UniFi; Italy) has been taking part in a joint project called “Strategies for Monitoring CO2 and other Gases in Natural analogues”. The group was coordinated by AMPHOS XXI, a private company established in Barcelona. The Project was financially supported by Fundación Ciudad de la Energía (CIUDEN; Spain) as a part of the EC-funded OXYCFB300 project (European Energy Program for Recovery -EEPR-; www.compostillaproject.eu). The main objectives of the project were aimed to develop and optimize analytical methodologies to be applied at the surface to Monitor and Verify the feasibility of geologically stored carbon dioxide. These techniques were oriented to detect and quantify possible CO2 leakages to the atmosphere. Several investigations were made in natural analogues from Spain and Italy and in the Tecnchnological Development Plant for CO2 injection al Hontomín (Burgos, Spain). The studying techniques were mainly focused on the measurements of diffuse soil gases and surface and shallow waters. The soil-gas measurements included the determination of CO2 flux and the application to natural trace gases (e.g. radon) that may help to detect any CO2 leakage. As far as the water chemistry is concerned, geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of the PDT of Hontomín were analyzed to determine the most suitable parameters to trace the migration of the injected CO2 into the near-surface environments. The accumulation chamber method was used to measure the diffuse emission of CO2 at the soil-atmosphere interface. Although this technique has widely been applied in different scientific areas, it was considered of the utmost importance to adapt the optimum methodology for measuring the CO2 soil flux and estimating the total CO2 output to the specific features of the site where CO2 is to be stored shortly. During the pre-injection phase CO2 fluxes are expected to be relatively low where in the intra- and post-injection phases, if leakages are to be occurring, small variation in CO2 flux might be detected when the CO2 “noise” is overcoming the biological activity of the soil (soil respiration). CO2 flux measurements by the accumulation chamber method could be performed without vegetation clearance or after vegetation clearance. However, the results obtained after clearance show less dispersion and this suggests that this procedure appears to be more suitable for monitoring CO2 Storage sites. The measurement protocol, applied for the determination of the CO2 flux baseline at Hontomín, has included the following steps: a) cleaning and removal of both the vegetal cover and top 2 cm of soil, b) waiting to reduce flux perturbation due to the soil removal and c) measuring the CO2 flux. Once completing the CO2 flux measurements and detected whether there were anomalies zones, the total CO2 output was estimated to quantify the amount of CO2 released to the atmosphere in each of the studied areas. There is a wide range of methodologies for the estimation of the CO2 output, which were applied to understand which one was the most representative. In this study six statistical methods are presented: arithmetic mean, minimum variances unbiased estimator, bootstrap resample, partitioning of data into different populations with a graphical and a maximum likelihood procedures, and sequential Gaussian simulation. Eight campaigns were carried out in the Hontomín CO2 Storage Technology Development Plant and in natural CO2 analogues. The results show that sequential Gaussian simulation is the most accurate method to estimate the total CO2 output and the confidential interval. Nevertheless, a variety of statistic methods were also used. As a consequence, an application procedure for selecting the most realistic method was developed. The first step to estimate the total emanation rate was the variogram analysis. If the relation among the data can be explained with the variogram, the best technique to calculate the total CO2 output and its confidence interval is the sequential Gaussian simulation method (sGs). If the data are independent, their distribution is to be analyzed. For normal and log-normal distribution the proper methods are the arithmetic mean and minimum variances unbiased estimator, respectively. If the data are not normal (log-normal) or are a mixture of different populations the best approach is the bootstrap resampling. According to these steps, the maximum confidence interval was about ±20/25%, with most of values between ±3.5% and ±8%. Partitioning of CO2 flux data into different populations may help to interpret the data as their distribution can be affected by different geochemical processes, e.g. geological or biological sources of CO2. Consequently, it may be an important tool in a monitoring CCS program, where the main goal is to demonstrate that there are not leakages from the reservoir to the atmosphere and, if occurring, to be able to detect and quantify it. Results show that the partitioning of populations is better performed by maximum likelihood criteria, since graphical procedures have a degree of subjectivity in the interpretation and results may not be reproducible. The relationship between CO2 flux and radon isotopes (222Rn and 220Rn) was studied in natural analogues. In all emissions zones, a positive relation between 222Rn and CO2 was observed. However, the relationship between activity of 220Rn and CO2 flux is not clear. In some cases the 220Rn activity indeed increased with the CO2 flux in other measurements a decrease was recognized. We can speculate that this effect was possibly related to the route (deep or shallow) of the radon source. These results may confirm the possible use of the radon isotopes as tracers for the gas origin and their application in the detection of leakages. With respect to the CO2 flux baseline at the TDP of Hontomín, soil flux measurements in the vicinity of oil boreholes, drilled in the eighties and named H-1 to H-4, and injection and monitoring wells were performed using an accumulation chamber. Seven surveys were carried out from November 2009 to summer 2011. More than 4,000 measurements were used to determine the baseline flux of CO2 and its seasonal variations. The measured values were relatively low (from 5 to 13 g•m-2•day-1) and few outliers were identified, mainly located close to the H-2 oil well. Nevertheless, these values cannot be associated to a deep source of CO2, being more likely related to biological processes, i.e. soil respiration. No anomalies were recognized close to the deep fault system (Ubierna Fault) detected by geophysical investigations. There, the CO2 flux is indeed as low as other measurement stations. CO2 fluxes appear to be controlled by the biological activity since the lowest values were recorded during autumn-winter seasons and they tend to increase in warm periods. Two reference CO2 flux values (UCL50 of 5 g•m-2•d-1 for non-ploughed areas in autumn-winter seasons and 3.5 and 12 g•m-2•d-1 for in ploughed and non-ploughed areas, respectively, in spring-summer time, and UCL99 of 26 g•m-2•d-1 for autumn-winter in not-ploughed areas and 34 and 42 g•m-2•d-1 for spring-summer in ploughed and not-ploughed areas, respectively, were calculated. Fluxes higher than these reference values could be indicative of possible leakage during the operational and post-closure stages of the storage project. The first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3 − composition, similar to that of the surface waters. Some spring waters are characterized by relatively high concentrations of NO3 − (up to 123 mg/L), unequivocally suggesting an anthropogenic source. Anomalous concentrations of Cl−, SO4 2−, As, B and Ba were measured in two springs, discharging a few hundred meters from the oil wells, and in the Rio Ubierna. These contents are possibly indicative of mixing processes between deep and shallow aquifers. The chemistry of the dissolved gases also evidences the shallow circuits of the Hontomín– Huermeces, mainly characterized by an atmospheric source as highlighted by the contents of N2, O2, Ar and their relative ratios. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of the surface and spring waters in the surroundings of Hontomín can be considered as background values when intra- and post-injection monitoring programs will be carried out. In this respect, main and minor solutes, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

Enhanced radon emission in natural CO2 flows in Campo de Calatrava region (central Spain)

Activity of radon gas in natural soils is commonly low (in the order of few thousands of Bq·m-3) due to the fast decay (half-life= 3.8 days in the case of 222Rn) that prevents accumulation in soil pores. Exceptionally, high Rn soil activity (up to 430 KBq·m-3) is found around point sources of deep CO2 fluxes. These fluxes allow the transport of trace gases (including Rn) to long distances in the geosphere leading to a potential hazard as Rn accumulation in buildings. CO2 degassing is common in active or ancient volcanic fields and occurs as free gas fluxes or dissolved in groundwater. In this work, the occurrence of Rnbearing, CO2 fluxes from the Campo de Calatrava region in Central Spain has been studied in order to determine their (1) magnitude, (2) migration paths and (3) potential impact on the environment, and (4) methodologies to best detection and measurement.

Origin and patterns of distribution of trace elements in street dust. Unleaded petrol and urban lead

The elemental composition, patterns of distribution and possible sources of street dust are not common to all urban environments, but vary according to the peculiarities of each city. The common features and dissimilarities in the origin and nature of street dust were investigated through a series of studies in two widely different cities, Madrid (Spain) and Oslo (Norway), between 1990 and 1994. The most comprehensive sampling campaign was carried out in the Norwegian capital during the summer of 1994. An area of 14 km2, covering most of downtown Oslo and some residential districts to the north of the city, was divided into 1 km2 mapping units, and 16 sampling increments of approximately 150 g were collected from streets and roads in each of them. The fraction below 100 μm was acid-digested and analysed by ICP-MS. Statistical analyses of the results suggest that chemical elements in street dust can be classified into three groups: “urban” elements (Ba, Cd, Co, Cu, Mg, Pb, Sb, Ti, Zn), “natural” elements (Al, Ga, La, Mn, Na, Sr, Th, Y) and elements of a mixed origin or which have undergone geochemical changes from their original sources (Ca, Cs, Fe, Mo, Ni, Rb, Sr, U). Soil resuspension and/or mobilisation appears to be the most important source of “natural” elements, while “urban” elements originate primarily from traffic and from the weathering and corrosion of building materials. The data for Pb seem to prove that the gradual shift from leaded to unleaded petrol as fuel for automobiles has resulted in an almost proportional reduction in the concentration of Pb in dust particles under 100 μm. This fact and the spatial distribution of Pb in the city strongly suggest that lead sources other than traffic (i.e. lead accumulated in urban soil over the years) may contribute as much lead, if not more, to urban street dust.

Atmospheric Propagation at 100 and 300 GHz: Assessment of a Method to Identify Rainy Conditions during Radiosoundings

The influence of atmospheric gases and tropospheric phenomena becomes more relevant at frequencies within the THz band (100 GHz to 10 THz), severely affecting the propagation conditions. The use of radiosoundings in propagation studies is a well established measurement technique in order to collect information about the vertical structure of the atmosphere, from which gaseous and cloud attenuation can be estimated with the use of propagation models. However, some of these prediction models are not suitable to be used under rainy conditions. In the present study, a method to identify the presence of rainy conditions during radiosoundings is introduced, with the aim of filtering out these events from yearly statistics of predicted atmospheric attenuation. The detection procedure is based on the analysis of a set of parameters, some of them extracted from synoptical observations of weather (SYNOP reports) and other derived from radiosonde observations (RAOBs). The performance of the method has been evaluated under different climatic conditions, corresponding to three locations in Spain, where colocated rain gauge data were available. Rain events detected by the method have been compared with those precipitations identified by the rain gauge. The pertinence Received 26 June 2012, Accepted 31 July 2012, Scheduled 15 August 2012 * Corresponding author: Gustavo Adolfo Siles Soria (gsiles@grc.ssr.upm.es). 258 Siles et al. of the method is discussed on the basis of an analysis of cumulative distributions of total attenuation at 100 and 300 GHz. This study demonstrates that the proposed method can be useful to identify events probably associated to rainy conditions. Hence, it can be considered as a suitable algorithm in order to filter out this kind of events from annual attenuation statistics.

New analysis and estimations of atmospheric attenuation at 100 GHz using meteorological data in Madrid

Atmospheric propagation at frequencies within the THz domain are deeply affected by the influence of the composition and phenomena of the troposphere. This paper is focused on the estimation of first order statistics of total attenuation under non-rainy conditions at 100 GHz. With this purpose, a yearly meteorological database from Madrid, including radiosoundings, SYNOP observations and co-site rain gauge, have been used in order to calculate attenuation due to atmospheric gases and clouds, as well as to introduce and evaluate a rain detection method. This method allows to filter out rain events and refine the statistics of total attenuation under the scenarios under study. It is expected that the behavior of the statistics would be closest to the ones obtained by experimental techniques under similar conditions.

Hydrogeochemistry of surface and spring waters in the surroundings of the CO2 injection site at Hontomín–Huermeces (Burgos, Spain)

In this paper the very first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. Hontomín–Huermeces has been selected as a pilot site for the injection of pure (>99%) CO2. Injection and monitoring wells are planned to be drilled close to 6 oil wells completed in the 1980s for which detailed stratigraphical logs are available, indicating the presence of a confined saline aquifer at the depth of about 1500 m into which less than 100,000 tons of iquid CO2 will be injected, possibly starting in 2013. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3− composition, similar to that of the surface waters. This is also supported by the oxygen and hydrogen isotopic ratios that have values lying between those of the Global and the Mediterranean Meteoric Water Lines. Some spring waters close to the oil wells are haracterized by relatively high concentrations of NO3− (up to 123 mg/L), unequivocally suggesting an anthropogenic source that adds to the main water–rock interaction processes. The latter can be referred to Ca-Mg-carbonate and, at a minor extent, Al-silicate dissolution, being the outcropping sedimentary rocks characterized by Palaeozoic to Quaternary rocks. Anomalous concentrations of Cl−, SO42−, As, B and Ba were measured in two springs discharging a few hundred meters from the oil wells and in the Rio Ubierna. These contents are significantly higher than those of the whole set of the studied waters and are possibly indicative of mixing processes, although at very low extent, between deep and shallow aquifers. No evidence of deep-seated gases interacting with the Hontomín–Huermeces waters was recognized in the chemistry of the disolved gases. This is likely due to the fact that they are mainly characterized by an atmospheric source as highlighted by the high contents of N2, O2 and Ar and by N2/Ar ratios that approach that of ASW (Air Saturated Water) and possibly masking any contribution related to a deep source. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of this work are of particular importance when a monitoring program will be established to verify whether CO2 leakages, induced by the injection of this greenhouse gas, may be affecting the quality of the waters in the shallow hydrological circuits at Hontomín–Huermeces. In this respect, carbonate chemistry, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

Simulación del accidente de SGTR en un PWR-W con TRACE para distintas metodologías de análisis determinista de seguridad

A Steam Generator Tube Rupture (SGTR) in a Pressurized Water Reactor (PWR) can lead to an atmospheric release bypassing the containment via the secondary system and exiting though the Pressurized Operating Relief Valves of the affected Steam Generator. That is why SGTR historically have been treated in a special way in the different Deterministic Safety Analysis (DSA), focusing on the radioactive release more than the possibility of core damage, as it is done in the other Loss of Coolant Accidents(LOCAs).

Water chemistry at Hontomín-Huermeces (Burgos, Spain): insights for a pre-, intra- and post-CO2 injection geochemical monitoring.

In this study, the very first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín-Huermeces (Burgos, Spain) are presented and discussed. Hontomín-Huermeces was selected as a pilot site for the injection of pure (>99 %) CO2. Injection and monitoring wells are planned to be drilled close to 6 oil wells completed in the 1980’s. Stratigraphical logs indicate the presence of a confined saline aquifer at the depth of about 1,500 m into which less than 100,000 tons of liquid CO2 will be injected, possibly starting in 2013. The chemical and isotopic features of the spring waters suggest the occurrence of a shallow aquifer having a Ca2+(Mg2+)-HCO3- composition, relatively low salinity (Total Dissolved Solids _800 mg/L) and a meteoric isotopic signature. Some spring waters close to the oil wells are characterized by relatively high concentrations of NO3- (up to 123 mg/L), unequivocally indicating anthropogenic contamination that adds to the main water-rock interaction processes. The latter can be referred to Ca-Mg-carbonate and, at a minor extent, Al-silicate dissolution, being the outcropping sedimentary rocks characterized by Palaeozoic to Quaternary rocks. Anomalous concentrations of Cl-, SO42-, As, B and Ba were measured in two springs discharging a few hundreds meters from the oil wells and in the Rio Ubierna, possibly indicative of mixing processes, although at very low extent, between deep and shallow aquifers. Gases dissolved in spring waters show relatively high concentrations of atmospheric species, such as N2, O2 and Ar, and isotopically negative CO2 (<-17.7 h V-PDB), likely related to a biogenic source, possibly masking any contribution related to a deep source. The geochemical and isotopic data of this study are of particular importance when a monitoring program will be established to verify whether CO2 leakages, induced by the injection of this greenhouse gas, may affect the quality of the waters of the shallow Hontomín-Huermeces hydrological circuit. In this respect, carbonate chemistry, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

An initial study on atmospheric pressure ion transport by laser ionization and electrostatic fields.

Laser ionization of mixtures of gases at atmospheric pressure and the subsequent transport through electrostatic field is studied. A prototype is designed to perform the transport and detection of the ions. Relevance of the composition of the mixture of gases and ionization parameters is shown

Urban trees and atmospheric pollutants in big cities: Effects in Madrid

Una investigación sobre la mejora de la contaminación del aire (CA) por medio de arbolado urbano se realizó en Madrid, una ciudad con casi 4 M de habitantes, 2,8 M de vehículos y casi 3 M de árboles de mantenimiento público. La mayoría de los árboles estaban en dos bosques periurbanos. Los 650.000 restantes era pies de alineación y parques. Los taxones estudiados fueron Platanus orientalis (97.205 árboles), Ulmus sp. (70.557), Pinus pinea (49.038), Aesculus hippocastanum (22.266), Cedrus sp. (13.678) y Quercus ilex (1.650), de calles y parques. Muestras foliares se analizaron en diferentes épocas del año, así como datos de contaminación por PM10 de 28 estaciones de medición de la contaminación durante 30 años, y también la intensidad del tráfico (IMD) en 2.660 calles. La acumulación de metales pesados (MP) sobre hojas y dentro de estas se estimó en relación con la CA y del suelo y la IMD del tráfico. La concentración media de Ba, Cd, Cr, Cu, Mn, Ni, Pb y Zn en suelo (materia seca) alcanzó: 489,5, 0,7, 49,4, 60,9, 460,9, 12,8, 155,9 y 190,3 mg kg-1 respectivamente. Los árboles urbanos, particularmente coníferas (debido a la mayor CA en invierno) contribuyen significativamente a mejorar la CA sobre todo en calles con alta IMD. La capacidad de las seis sp. para capturar partículas de polvo en su superficies foliares está relacionada con la IMD del tráfico y se estimó en 16,8 kg/año de MP tóxicos. Pb y Zn resultaron ser buenos marcadores antrópicos en la ciudad en relación con el tráfico, que fue la principal fuente de contaminación en los árboles y suelos de Madrid. Las especies de árboles variaron en función de su capacidad para capturar partículas (dependiendo de las propiedades de sus superficies foliares) y acumular los MP absorbidos de los suelos. Las concentraciones foliares de Pb y Zn estuvieron por encima de los límites establecidos en diferentes sitios de la ciudad. La microlocalización de Zn mediante microscópico mostró la translocación al xilema y floema. Se detectaron puntos de contaminación puntual de Cu and Cr en antiguos polígonos industriales y la distribución espacial de los MP en los suelos de Madrid mostró que en incluso en zonas interiores del El Retiro había ciertos niveles elevados de [Pb] en suelo, tal vez por el emplazamiento la Real Fábrica de Porcelana en la misma zona hace 200 años. Distintas áreas del centro de la ciudad también alcanzaron niveles altos de [Pb] en suelo. Según los resultados, el empleo de una combinación de Pinus pinea con un estrato intermedio de Ulmus sp. y Cedrus sp. puede ser la mejor recomendación como filtro verde eficiente. El efecto del ozono (O3) sobre el arbolado en Madrid fue también objeto de este estudio. A pesar de la reducción de precursores aplicada en muchos países industrializados, O3 sigue siendo la principal causa de CA en el hemisferio norte, con el aumento de [O3] de fondo. Las mayores [O3] se alcanzaron en regiones mediterráneas, donde el efecto sobre la vegetación natural es compensado por el xeromorfismo y la baja conductancia estomática en respuesta los episodios de sequía estival característicos de este clima. Durante una campaña de monitoreo, se identificaron daños abióticos en hojas de encina parecidos a los de O3 que estaban plantadas en una franja de césped con riego del centro de Madrid. Dada la poca evidencia disponible de los síntomas de O3 en frondosas perennifolias, se hizo un estudio que trató de 1) confirman el diagnóstico de daño de O3, 2) investigar el grado de los síntomas en encinas y 3) analizar los factores ambientales que contribuyeron a los daños por O3, en particular en lo relacionado con el riego. Se analizaron los marcadores macro y micromorfológicos de estrés por O3, utilizando las mencionadas encinas a modo de parcela experimental. Los síntomas consistieron en punteado intercostal del haz, que aumentó con la edad. Además de un punteado subyacente, donde las células superiores del mesófilo mostraron reacciones características de daños por O3. Las células próximas a las zonas dañadas, presentaron marcadores adicionales de estrés oxidativo. Estos marcadores morfológicos y micromorfológicos de estrés por O3 fueron similares a otras frondosas caducifolias con daños por O3. Sin embargo, en nuestro caso el punteado fue evidente con AOT40 de 21 ppm•h, asociada a riego. Análisis posteriores mostraron que los árboles con riego aumentaron su conductancia estomática, con aumento de senescencia, manteniéndose sin cambios sus características xeromórficas foliares. Estos hallazgos ponen de relieve el papel primordial de la disponibilidad de agua frente a las características xeromórficas a la hora de manifestarse los síntomas en las células por daños de O3 en encina. ABSTRACT Research about air pollution mitigation by urban trees was conducted in Madrid (Spain), a southern European city with almost 4 M inhabitants, 2.8 M daily vehicles and 3 M trees under public maintenance. Most trees were located in two urban forests, while 650'000 trees along urban streets and in parks. The urban taxa included Platanus orientalis (97'205 trees), Ulmus sp. (70’557), Pinus pinea (49'038), Aesculus hippocastanum (22’266), Cedrus sp. (13'678 and Quercus ilex (1'650) along streets and parks. Leave samples were analysed sequentially in different seasons, PM10 data from 28 air monitoring stations during 30 years and traffic density estimated from 2’660 streets. Heavy metal (HM) accumulation on the leaf surface and within leaves was estimated per tree related to air and soil pollution, and traffic intensity. Mean concentration of Ba, Cd, Cr, Cu, Mn, Ni, Pb and Zn in topsoil samples (dry mass) amounted in Madrid: 489.5, 0.7, 49.4, 60.9, 460.9, 12.8, 155.9 and 190.3 mg kg-1 respectively. Urban trees, particularly conifers (due to higher pollution in winter) contributed significantly to alleviate air pollution especially near to high ADT roads. The capacity of the six urban street trees species to capture air-born dust on the foliage surface as related to traffic intensity was estimated to 16.8 kg of noxious metals from exhausts per year. Pb and Zn pointed to be tracers of anthropic activity in the city with vehicle traffic as the main source of diffuse pollution on trees and soils. Tree species differed by their capacity to capture air-borne dust (by different leaf surface properties) and to allocate HM from soils. Pb and Zn concentrations in the foliage were above limits in different urban sites and microscopic Zn revelation showed translocation in xylem and phloem tissue. Punctual contamination in soils by Cu and Cr was identified in former industrial areas and spatial trace element mapping showed for central Retiro Park certain high values of [Pb] in soils even related to a Royal pottery 200 years ago. Different areas in the city centre also reached high levels [Pb] in soils. According to the results, a combination of Pinus pinea with understorey Ulmus sp. and Cedrus sp. layers can be recommended for the best air filter efficiency. The effects of ozone (O3) on trees in different areas of Madrid were also part of this study. Despite abatement programs of precursors implemented in many industrialized countries, ozone remained the main air pollutant throughout the northern hemisphere with background [O3] increasing. Some of the highest ozone concentrations were measured in regions with a Mediterranean climate but the effect on the natural vegetation is alleviated by low stomatal uptake and frequent leaf xeromorphy in response to summer drought episodes characteristic of this climate. During a bioindication survey, abiotic O3-like injury was identified in foliage. Trees were growing on an irrigated lawn strip in the centre of Madrid. Given the little structural evidence available for O3 symptoms in broadleaved evergreen species, a study was undertaken in 2007 with the following objectives 1) confirm the diagnosis, 2) investigate the extent of symptoms in holm oaks growing in Madrid and 3) analyse the environmental factors contributing to O3 injury, particularly, the site water supply. Therefore, macro- and micromorphological markers of O3 stress were analysed, using the aforementioned lawn strip as an intensive study site. Symptoms consisted of adaxial and intercostal stippling increasing with leaf age. Underlying stippling, cells in the upper mesophyll showed HR-like reactions typical of ozone stress. The surrounding cells showed further oxidative stress markers. These morphological and micromorphological markers of ozone stress were similar to those recorded in deciduous broadleaved species. However, stippling became obvious already at an AOT40 of 21 ppm•h and was primarily found at irrigated sites. Subsequent analyses showed that irrigated trees had their stomatal conductance increased and leaf life-span reduced whereas their leaf xeromorphy remained unchanged. These findings suggest a central role of water availability versus leaf xeromorphy for ozone symptom expression by cell injury in holm oak.

Nueva tecnología para la separación de gases atmosféricos y captura de dióxido de carbono por aplicación de campos electromagnéticos y fotoionización

Son numerosos los expertos que predicen que hasta pasado 2050 no se utilizarán masivamente las energías de origen renovable, y que por tanto se mantendrá la emisión de dióxido de carbono de forma incontrolada. Entre tanto, y previendo que este tipo de uso se mantenga hasta un horizonte temporal aún más lejano, la captura, concentración y secuestro o reutilización de dióxido de carbono es y será una de las principales soluciones a implantar para paliar el problema medioambiental causado. Sin embargo, las tecnologías existentes y en desarrollo de captura y concentración de este tipo de gas, presentan dos limitaciones: las grandes cantidades de energía que consumen y los grandes volúmenes de sustancias potencialmente dañinas para el medioambiente que producen durante su funcionamiento. Ambas razones hacen que no sean atractivas para su implantación y uso de forma extensiva. La solución planteada en la presente tesis doctoral se caracteriza por la ausencia de residuos producidos en la operación de captura y concentración del dióxido de carbono, por no utilizar substancias químicas y físicas habituales en las técnicas actuales, por disminuir los consumos energéticos al carecer de sistemas móviles y por evitar la regeneración química y física de los materiales utilizados en la actualidad. Así mismo, plantea grandes retos a futuras innovaciones sobre la idea propuesta que busquen fundamentalmente la disminución de la energía utilizada durante su funcionamiento y la optimización de sus componentes principales. Para conseguir el objetivo antes citado, la presente tesis doctoral, una vez establecido el planteamiento del problema al que se busca solución (capítulo 1), del estudio de las técnicas de separación de gases atmosféricos utilizadas en la actualidad, así como del de los sistemas fundamentales de las instalaciones de captura y concentración del dióxido de carbono (capítulo 2) y tras una definición del marco conceptual y teórico (capítulo 3), aborda el diseño de un prototipo de ionización fotónica de los gases atmosféricos para su posterior separación electrostática, a partir del estudio, adaptación y mejora del funcionamiento de los sistemas de espectrometría de masas. Se diseñarán y desarrollarán los sistemas básicos de fotoionización, mediante el uso de fuentes de fotones coherentes, y los de separación electrostática (capítulo 4), en que se basa el funcionamiento de este sistema de separación de gases atmosféricos y de captura y concentración de dióxido de carbono para construir un prototipo a nivel laboratorio. Posteriormente, en el capítulo 5, serán probados utilizando una matriz experimental que cubra los rangos de funcionamiento previstos y aporte suficientes datos experimentales para corregir y desarrollar el marco teórico real, y con los que se pueda establecer y corregir un modelo físico– matemático de simulación (capítulo 6) aplicable a la unidad en su conjunto. Finalmente, debido a la utilización de unidades de ionización fotónica, sistemas láseres intensos y sistemas eléctricos de gran potencia, es preciso analizar el riesgo biológico a las personas y al medioambiente debido al impacto de la radiación electromagnética producida (capítulo 7), minimizando su impacto y cumpliendo con la legislación vigente. En el capítulo 8 se planteará un diseño escalable a tamaño piloto de la nueva tecnología propuesta y sus principales modos de funcionamiento, así como un análisis de viabilidad económica. Como consecuencia de la tesis doctoral propuesta y del desarrollo de la unidad de separación atmosférica y de captura y concentración de dióxido de carbono, surgen diversas posibilidades de estudio que pueden ser objeto de nuevas tesis doctorales y de futuros desarrollos de ingeniería. El capítulo 9 tratará de incidir en estos aspectos indicando líneas de investigación para futuras tesis y desarrollos industriales. ABSTRACT A large number of experts predict that until at least 2050 renewable energy sources will not be massively used, and for that reason, current Primary Energy sources based on extensive use of fossil fuel will be used maintaining out of control emissions, Carbon Dioxide above all. Meanwhile, under this scenario and considering its extension until at least 2050, Carbon Capture, Concentration, Storage and/or Reuse is and will be one of the main solutions to minimise Greenhouse Gasses environmental effect. But, current Carbon Capture and Storage technology state of development has two main problems: it is a too large energy consuming technology and during normal use it produces a large volume of environmentally dangerous substances. Both reasons are limiting its development and its extensive use. This Ph Degree Thesis document proposes a solution to get the expected effect using a new atmospheric gasses separation system with the following characteristics: absence of wastes produced, it needs no chemical and/or physical substances during its operation, it reduces to minimum the internal energy consumptions due to absence of mobile equipment and it does not need any chemical and/or physical regeneration of substances. This system is beyond the State of the Art of current technology development. Additionally, the proposed solution raises huge challenges for future innovations of the proposed idea finding radical reduction of internal energy consumption during functioning, as well as regarding optimisation of main components, systems and modes of operation. To achieve this target, once established the main problem, main challenge and potential solving solutions (Chapter 1), it is established an initial starting point fixing the Atmospheric Gasses Separation and Carbon Capture and Storage developments (Chapter 2), as well as it will be defined the theoretical and basic model, including existing and potential new governing laws and mathematical formulas to control its system functioning (Chapter 3), this document will deal with the design of an installation of an operating system based on photonic ionization of atmospheric gasses to be separated in a later separation system based on the application of electrostatic fields. It will be developed a basic atmospheric gasses ionization prototype based on intense radioactive sources capable to ionize gasses by coherent photonic radiation, and a basic design of electrostatic separation system (Chapter 4). Both basic designs are the core of the proposed technology that separates Atmospheric Gasses and captures and concentrates Carbon Dioxide. Chapter 5 will includes experimental results obtained from an experimental testing matrix covering expected prototype functioning regimes. With the obtained experimental data, theoretical model will be corrected and improved to act as the real physical and mathematical model capable to simulate real system function (Chapter 6). Finally, it is necessary to assess potential biological risk to public and environment due to the proposed use of units of intense energy photonic ionization, by laser beams or by non–coherent sources and large electromagnetic systems with high energy consumption. It is necessary to know the impact in terms of and electromagnetic radiation taking into account National Legislation (Chapter 7). On Chapter 8, an up scaled pilot plant will be established covering main functioning modes and an economic feasibility assessment. As a consequence of this PhD Thesis, a new field of potential researches and new PhD Thesis are opened, as well as future engineering and industrial developments (Chapter 9).