Shallow water marine sediment bacterial community shifts along a natural CO2 gradient in the Mediterranean Sea Off vulcano, Italy

The effects of increasing atmospheric CO(2) on ocean ecosystems are a major environmental concern, as rapid shoaling of the carbonate saturation horizon is exposing vast areas of marine sediments to corrosive waters worldwide. Natural CO(2) gradients off Vulcano, Italy, have revealed profound ecosystem changes along rocky shore habitats as carbonate saturation levels decrease, but no investigations have yet been made of the sedimentary habitat. Here, we sampled the upper 2 cm of volcanic sand in three zones, ambient (median pCO(2) 419 µatm, minimum Omega (arag) 3.77), moderately CO(2)-enriched (median pCO(2) 592 µatm, minimum Omega (arag) 2.96), and highly CO(2)-enriched (median pCO(2) 1611 µatm, minimum Omega (arag) 0.35). We tested the hypothesis that increasing levels of seawater pCO(2) would cause significant shifts in sediment bacterial community composition, as shown recently in epilithic biofilms at the study site. In this study, 454 pyrosequencing of the V1 to V3 region of the 16S rRNA gene revealed a shift in community composition with increasing pCO(2). The relative abundances of most of the dominant genera were unaffected by the pCO(2) gradient, although there were significant differences for some 5 % of the genera present (viz. Georgenia, Lutibacter, Photobacterium, Acinetobacter, and Paenibacillus), and Shannon Diversity was greatest in sediments subject to long-term acidification (>100 years). Overall, this supports the view that globally increased ocean pCO(2) will be associated with changes in sediment bacterial community composition but that most of these organisms are resilient. However, further work is required to assess whether these results apply to other types of coastal sediments and whether the changes in relative abundance of bacterial taxa that we observed can significantly alter the biogeochemical functions of marine sediments.

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.

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.

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.

Co2 capture in power plants-using the oxy-combustion principle

In the C02 capture from power generation, the energy penalties for the capture are one of the main challenges. Nowadays, the post-combustion methods have energy penalties 10wer than the oxy combustion and pre-combustion technologies. One of the main disadvantages of the post combustion method is the fact that the capture ofC02at atmospheric pressure requires quite big equipment for the high flow rates of flue gas, and the 10w partial pressure of the CO2generates an important 10ss of energy. The A1lam cyc1e presented for NETPOWER gives high efficiencies in the power production and 10w energy penalties. A simulation of this cyc1e is made together with a simulation of power plants with pre-combustion and post-combustion capture and without capture for natural gas and forcoa1. The simulations give 10wer efficiencies than the proposed for NETPOWER For natural gas the efficiency is 52% instead of the 59% presented, and 33% instead of51% in the case of using coal as fuel. Are brought to light problems in the CO2compressor due the high flow ofC02that is compressed unti1300 bar to be recyc1ed into the combustor.

The origin of atmospheric oxygen on Earth: The innovation of oxygenic photosynthesis

The evolution of O2-producing cyanobacteria that use water as terminal reductant transformed Earth's atmosphere to one suitable for the evolution of aerobic metabolism and complex life. The innovation of water oxidation freed photosynthesis to invade new environments and visibly changed the face of the Earth. We offer a new hypothesis for how this process evolved, which identifies two critical roles for carbon dioxide in the Archean period. First, we present a thermodynamic analysis showing that bicarbonate (formed by dissolution of CO2) is a more efficient alternative substrate than water for O2 production by oxygenic phototrophs. This analysis clarifies the origin of the long debated “bicarbonate effect” on photosynthetic O2 production. We propose that bicarbonate was the thermodynamically preferred reductant before water in the evolution of oxygenic photosynthesis. Second, we have examined the speciation of manganese(II) and bicarbonate in water, and find that they form Mn-bicarbonate clusters as the major species under conditions that model the chemistry of the Archean sea. These clusters have been found to be highly efficient precursors for the assembly of the tetramanganese-oxide core of the water-oxidizing enzyme during biogenesis. We show that these clusters can be oxidized at electrochemical potentials that are accessible to anoxygenic phototrophs and thus the most likely building blocks for assembly of the first O2 evolving photoreaction center, most likely originating from green nonsulfur bacteria before the evolution of cyanobacteria.

Direct observation of the oceanic CO2 increase revisited

We show, from recent data obtained at specimen North Pacific stations, that the fossil fuel CO2 signal is strongly present in the upper 400 m, and that we may consider areal extrapolations from geochemical surveys to determine the magnitude of ocean fossil fuel CO2 uptake. The debate surrounding this topic is illustrated by contrasting reports which suggest, based upon atmospheric observations and models, that the oceanic CO2 sink is small at these latitudes; or that the oceanic CO2 sink, based upon oceanic data and models, is large. The difference between these two estimates is at least a factor of two. There are contradictions arising from estimates based on surface partial pressures of CO2 alone, where the signal sought is small compared with regional and seasonal variability; and estimates of the accumulated subsurface burden, which correlates well other oceanic tracers. Ocean surface waters today contain about 45 μmol⋅kg−1 excess CO2 compared with those of the preindustrial era, and the signal is rising rapidly. What limits should we place on such calculations? The answer lies in the scientific questions to be asked. Recovery of the fossil fuel CO2 contamination signal from analysis of ocean water masses is robust enough to permit reasonable budget estimates. However, because we do not have sufficient data from the preindustrial ocean, the estimation of the required Redfield oxidation ratio in the upper several hundred meters is already blurred by the very fossil fuel CO2 signal we seek to resolve.

Estudo do processo de absorção e dessorção de CO2 na solução aquosa de metildietanolamina e piperazina.

Estudou-se o processo de absorção e dessorção de CO2 em solução aquosa da mistura de metildietanolamina (MDEA) e piperazina (PZ). Os ensaios de absorção foram realizados numa coluna de parede molhada com promotor de película, e, os ensaios de dessorção num sistema de semibatelada, ambos em escala de laboratório. Os testes experimentais de absorção foram realizados a 298 K e pressão atmosférica, com vazão de gás (CO2 e ar atmosférico) de 2,2.10-4 m3 s-1 e as seguintes vazões de líquido: 1,0.10-6; 1,3.10-6 e 1,7.10-6 m3 s-1. O sistema de absorção foi caracterizado através da determinação da área interfacial, a, o coeficiente volumétrico de transferência de massa, kGa, e o coeficiente volumétrico global médio de transferência de massa, KGa. No caso dos ensaios de dessorção, estes foram realizados nas temperaturas de 353, 363 e 368 K, onde empregou-se uma solução carbonatada de 10% PZ-20% MDEA e uma corrente de ar atmosférico nas vazões de 1,1.10-5 m3 s-1 e 2,7.10-5 m3 s-1. Este sistema foi caracterizado através da determinação do coeficiente volumétrico global de transferência de massa, KLa. Os resultados experimentais da área interfacial mostram que este é função da vazão do líquido, sugerindo uma maior área de irrigação como o aumento desta, onde teve-se uma maior área de transferência de massa. O resultado do parâmetro, KGa, indica uma dependência da vazão de líquido, a qual está associada à variação da área interfacial e à dependência do parâmetro KG com o perfil das concentrações da MDEA e PZ ao longo da coluna. A partir da teoria do duplo filme e pelo conhecimento dos parâmetros KGa, a e kGa, estimou-se um parâmetro cinético-difusivo associado à fase líquida, (( ) ) . Os resultados experimentais mostram que esse parâmetro varia pouco com a vazão de líquido, indicando tratar-se de um processo independente da hidrodinâmica do líquido, característico de sistemas com reação rápida. A concentração das aminas e carbamatos, nos ensaios de absorção e dessorção, foi determinada através dos modelos de calibração obtidas pela técnica de espectroscopia no infravermelho. Nos ensaios de absorção, foram observados que a concentração de PZ teve uma variação considerável (4 a 5% massa massa-1), entanto que a de MDEA variou pouco (0,3 a 0,5% massa massa-1), sugerindo que o processo de absorção de CO2 na mistura MDEA-PZ é controlado principalmente pela PZ, e supõe-se que a MDEA tem um papel de receptor de prótons procedentes da reação entre a PZ e o CO2. Nos ensaios de dessorção, observou-se que esse processo é afetado pela temperatura, sendo que, em temperaturas perto da ebulição (372 K), a taxa de dessorção de CO2 é maior do que em temperaturas menores, em certa forma é devido à dependência da velocidade de reação química com a temperatura. Os resultados do parâmetro KLa indicam que este diminui em função da concentração de carbamato de PZ (por exemplo, na temperatura de 368 K, de 7,5.10-4 a 1,0.10-4 s-1), devido a que este componente é decomposto em altas temperaturas gerando o CO2 e as aminas, sugerindo uma diminuição na velocidade de dessorção de CO2. Assim também, os resultados experimentais do parâmetro KLa indicam que este aumenta ligeiramente com a vazão do gás.

High selectivity of TiC-CDC for CO2/N2 separation

A series of carbide-derived carbons (CDC) have been prepared starting from TiC and using different chlorine treatment temperatures (500–1200 °C). Contrary to N2 adsorption measurements at −196 °C, CO2 adsorption measurements at room temperature and high pressure (up to 1 MPa) together with immersion calorimetry measurements into dichloromethane suggest that the synthesized CDC exhibit a similar porous structure, in terms of narrow pore volume, independently of the temperature of the reactive extraction treatment used (samples synthesized below 1000 °C). Apparently, these carbide-derived carbons exhibit narrow constrictions were CO2 adsorption under standard conditions (0 °C and atmospheric pressure) is kinetically restricted. The same accounts for a slightly larger molecule as N2 at a lower adsorption temperature (−196 °C), i.e. textural parameters obtained from N2 adsorption measurements on CDC must be underestimated. Furthermore, here we show experimentally that nitrogen exhibits an unusual behavior, poor affinity, on these carbide-derived carbons. CH4 with a slightly larger diameter (0.39 nm) is able to partially access the inner porous structure whereas N2, with a slightly smaller diameter (0.36 nm), does not. Consequently, these CDC can be envisaged as excellent sorbent for selective CO2 capture in flue-gas streams.