Aquaponics: integrating fish feeding rates and ion waste production for strawberry hydroponics

Aquaponics is the science of integrating intensive fish aquaculture with plant production in recirculating water systems. Although ion waste production by fish cannot satisfy all plant requirements, less is known about the relationship between total feed provided for fish and the production of milliequivalents (mEq) of different macronutrients for plants, especially for nutrient flow hydroponics used for strawberry production in Spain. That knowledge is essential to consider the amount of macronutrients available in aquaculture systems so that farmers can estimate how much nutrient needs to be supplemented in the waste water from fish, to produce viable plant growth. In the present experiment, tilapia (Oreochromis niloticus L.) were grown in a small-scale recirculating system at two different densities while growth and feed consumption were noted every week for five weeks. At the same time points, water samples were taken to measure pH, EC25, HCO3 – , Cl – , NH4 + , NO2 – , NO3 – , H2PO4 – , SO4 2– , Na + , K+ , Ca 2+ and Mg 2+ build up. The total increase in mEq of each ion per kg of feed provided to the fish was highest for NO3 - , followed, in decreasing order, by Ca 2+ , H2PO4 – , K+ , Mg 2+ and SO4 2– . The total amount of feed required per mEq ranged from 1.61- 13.1 kg for the four most abundant ions (NO3 – , Ca 2+ , H2PO4 – and K+ ) at a density of 2 kg fish m–3 , suggesting that it would be rather easy to maintain small populations of fish to reduce the cost of hydroponic solution supplementation for strawberries.

Impact of nitrogen uptake on field water balance in fertirrigated melon.

Agronomic management in Ciudad Real, a province in central Spain, is characteristic of semi-arid cropped areas whose water supplies have high nitrate (NO3?) content due to environmental degradation. This situation is aggravated by the existence of a restrictive subsurface layer of ?caliche? or hardpan at a depth of 0.60 m. Under these circumstances, fertirrigation rates, including nitrogen (N) fertilizer schedules, must be carefully calibrated to optimize melon yields while minimizing the N pollution and water supply. Such optimization was sought by fertilizing with different doses of N and irrigating at 100% of the ETc (crop evapotranspiration), adjusted for this crop and area. The N content in the four fertilizer doses used was: 0, 55, 82 and 109 kg N ha?1. Due to the NO3? content in the irrigation water, however, the actual N content was 30 kg ha?1 higher in all four treatments repeated in two different years. The results showed correlation between melon plant N uptake and drainage (Dr), which in turn affects the amount of N leached, as well as correlation between Dr and LAI (leaf area index) for each treatment. A fertilizer factor (?) was estimated through two methods, from difference in Dr and in LAI ratio with respect to the maximum N dose, to correct ETc based on N doses. The difference was found in the adjusted evapotranspiration in both years using the corresponding ? achieved 42?49 mm at vegetative period, depending on the method, and it was not significant at senescent period. Finally, a growth curve between N uptake and plant dry weight (DW) for each treatment was defined to confirm that the observed higher plant vigour, showing higher LAI and reduced Dr, was due mainly to higher N doses.

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.

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.

The potential of organic fertilizers and water management to reduce N2O emissions in Mediterranean climate cropping systems. A review.

Environmental problems related to the use of synthetic fertilizers and to organic waste management have led to increased interest in the use of organic materials as an alternative source of nutrients for crops, but this is also associated with N2O emissions. There has been an increasing amount of research into the effects of using different types of fertilization on N2O emissions under Mediterranean climatic conditions, but the findings have sometimes been rather contradictory. Available information also suggests that water management could exert a high influence on N2O emissions. In this context, we have reviewed the current scientific knowledge, including an analysis of the effect of fertilizer type and water management on direct N2O emissions. A meta-analysis of compliant reviewed experiments revealed significantly lower N2O emissions for organic as opposed to synthetic fertilizers (23% reduction). When organic materials were segregated in solid and liquid, only solid organic fertilizer emissions were significantly lower than those of synthetic fertilizers (28% reduction in cumulative emissions). The EF is similar to the IPCC factor in conventionally irrigated systems (0.98% N2O-N N applied−1), but one order of magnitude lower in rainfed systems (0.08%). Drip irrigation produces intermediate emission levels (0.66%). Differences are driven by Mediterranean agro-climatic characteristics, which include low soil organic matter (SOM) content and a distinctive rainfall and temperature pattern. Interactions between environmental and management factors and the microbial processes involved in N2O emissions are discussed in detail. Indirect emissions have not been fully accounted for, but when organic fertilizers are applied at similar N rates to synthetic fertilizers, they generally make smaller contributions to the leached NO3− pool. The most promising practices for reducing N2O through organic fertilization include: (i) minimizing water applications; (ii) minimizing bare soil; (iii) improving waste management; and (iv) tightening N cycling through N immobilization. The mitigation potential may be limited by: (i) residual effect; (ii) the long-term effects of fertilizers on SOM; (iii) lower yield-scaled performance; and (iv) total N availability from organic sources. Knowledge gaps identified in the review included: (i) insufficient sampling periods; (ii) high background emissions; (iii) the need to provide N2O EF and yield-scaled EF; (iv) the need for more research on specific cropping systems; and (v) the need for full GHG balances. In conclusion, the available information suggests a potential of organic fertilizers and water-saving practices to mitigate N2O emissions under Mediterranean climatic conditions, although further research is needed before it can be regarded as fully proven, understood and developed.

N2O emissions and N efficiency due to tillage systems and crop rotation under a rainfed Mediterranean agroecosystem

Application of nitrogen (N) fertilizers in agricultural soils increases the risk of N loss to the atmosphere in the form of ammonia (NH3), nitrous oxide (N2O) and nitric oxide (NO)and the water bodies as nitrate (NO3-). The implementation of agricultural management practices can affect these losses. In Mediterranean irrigation systems, the greatest losses of NO3-through leaching occur within the irrigation and the intercropperiod. One way to abate these losses during the intercrop period is the use of cover crops that absorb part of the residual N from the root zone (Gabriel and Quemada, 2011). Moreover, during the following crop, these species could be applied as amendments to the soil, providing both C and N to the soil. This effect of cover and catch crops on decreasing the pool of N potentially lost has focused primarily on NO3-leaching. The aim of this work was to evaluate the effect of cover crops on N2O emission during the in tercrop period in a maize system and its subsequent incorporation into the soil in the following maize crop.

Fertilization Management: Assessing New Techniques and Key Interactions to Increase Crop Yields With Less N2O Emissions

El óxido nitroso (N2O) es un potente gas de efecto invernadero (GHG) proveniente mayoritariamente de la fertilización nitrogenada de los suelos agrícolas. Identificar estrategias de manejo de la fertilización que reduzcan estas emisiones sin suponer un descenso de los rendimientos es vital tanto a nivel económico como medioambiental. Con ese propósito, en esta Tesis se han evaluado: (i) estrategias de manejo directo de la fertilización (inhibidores de la nitrificación/ureasa); y (ii) interacciones de los fertilizantes con (1) el manejo del agua, (2) residuos de cosecha y (3) diferentes especies de plantas. Para conseguirlo se llevaron a cabo meta-análisis, incubaciones de laboratorio, ensayos en invernadero y experimentos de campo. Los inhibidores de la nitrificación y de la actividad ureasa se proponen habitualmente como medidas para reducir las pérdidas de nitrógeno (N), por lo que su aplicación estaría asociada al uso eficiente del N por parte de los cultivos (NUE). Sin embargo, su efecto sobre los rendimientos es variable. Con el objetivo de evaluar en una primera fase su efectividad para incrementar el NUE y la productividad de los cultivos, se llevó a cabo un meta-análisis. Los inhibidores de la nitrificación dicyandiamide (DCD) y 3,4-dimetilepyrazol phosphate (DMPP) y el inhibidor de la ureasa N-(n-butyl) thiophosphoric triamide (NBPT) fueron seleccionados para el análisis ya que generalmente son considerados las mejores opciones disponibles comercialmente. Nuestros resultados mostraron que su uso puede ser recomendado con el fin de incrementar tanto el rendimiento del cultivo como el NUE (incremento medio del 7.5% y 12.9%, respectivamente). Sin embargo, se observó que su efectividad depende en gran medida de los factores medioambientales y de manejo de los estudios evaluados. Una mayor respuesta fue encontrada en suelos de textura gruesa, sistemas irrigados y/o en cultivos que reciben altas tasas de fertilizante nitrogenado. En suelos alcalinos (pH ≥ 8), el inhibidor de la ureasa NBPT produjo el mayor efecto. Dado que su uso representa un coste adicional para los agricultores, entender las mejores prácticas que permitan maximizar su efectividad es necesario para posteriormente realizar comparaciones efectivas con otras prácticas que incrementen la productividad de los cultivos y el NUE. En base a los resultados del meta-análisis, se seleccionó el NBPT como un inhibidor con gran potencial. Inicialmente desarrollado para reducir la volatilización de amoniaco (NH3), en los últimos años algunos investigadores han demostrado en estudios de campo un efecto mitigador de este inhibidor sobre las pérdidas de N2O provenientes de suelos fertilizados bajo condiciones de baja humedad del suelo. Dada la alta variabilidad de los experimentos de campo, donde la humedad del suelo cambia rápidamente, ha sido imposible entender mecanísticamente el potencial de los inhibidores de la ureasa (UIs) para reducir emisiones de N2O y su dependencia con respecto al porcentaje de poros llenos de agua del suelo (WFPS). Por lo tanto se realizó una incubación en laboratorio con el propósito de evaluar cuál es el principal mecanismo biótico tras las emisiones de N2O cuando se aplican UIs bajo diferentes condiciones de humedad del suelo (40, 60 y 80% WFPS), y para analizar hasta qué punto el WFPS regula el efecto del inhibidor sobre las emisiones de N2O. Un segundo UI (i.e. PPDA) fue utilizado para comparar el efecto del NBPT con el de otro inhibidor de la ureasa disponible comercialmente; esto nos permitió comprobar si el efecto de NBPT es específico de ese inhibidor o no. Las emisiones de N2O al 40% WFPS fueron despreciables, siendo significativamente más bajas que las de todos los tratamientos fertilizantes al 60 y 80% WFPS. Comparado con la urea sin inhibidor, NBPT+U redujo las emisiones de N2O al 60% WFPS pero no tuvo efecto al 80% WFPS. La aplicación de PPDA incrementó significativamente las emisiones con respecto a la urea al 80% WFPS mientras que no se encontró un efecto significativo al 60% WFPS. Al 80% WFPS la desnitrificación fue la principal fuente de las emisiones de N2O en todos los tratamientos mientras que al 60% tanto la nitrificación como la desnitrificación tuvieron un papel relevante. Estos resultados muestran que un correcto manejo del NBPT puede suponer una estrategia efectiva para mitigar las emisiones de N2O. Con el objetivo de trasladar nuestros resultados de los estudios previos a condiciones de campo reales, se desarrolló un experimento en el que se evaluó la efectividad del NBPT para reducir pérdidas de N y aumentar la productividad durante un cultivo de cebada (Hordeum vulgare L.) en secano Mediterráneo. Se determinó el rendimiento del cultivo, las concentraciones de N mineral del suelo, el carbono orgánico disuelto (DOC), el potencial de desnitrificación, y los flujos de NH3, N2O y óxido nítrico (NO). La adición del inhibidor redujo las emisiones de NH3 durante los 30 días posteriores a la aplicación de urea en un 58% y las emisiones netas de N2O y NO durante los 95 días posteriores a la aplicación de urea en un 86 y 88%, respectivamente. El uso de NBPT también incrementó el rendimiento en grano en un 5% y el consumo de N en un 6%, aunque ninguno de estos incrementos fue estadísticamente significativo. Bajo las condiciones experimentales dadas, estos resultados demuestran el potencial del inhibidor de la ureasa NBPT para mitigar las emisiones de NH3, N2O y NO provenientes de suelos arables fertilizados con urea, mediante la ralentización de la hidrólisis de la urea y posterior liberación de menores concentraciones de NH4 + a la capa superior del suelo. El riego por goteo combinado con la aplicación dividida de fertilizante nitrogenado disuelto en el agua de riego (i.e. fertirriego por goteo) se considera normalmente una práctica eficiente para el uso del agua y de los nutrientes. Algunos de los principales factores (WFPS, NH4 + y NO3 -) que regulan las emisiones de GHGs (i.e. N2O, CO2 y CH4) y NO pueden ser fácilmente manipulados por medio del fertirriego por goteo sin que se generen disminuciones del rendimiento. Con ese propósito se evaluaron opciones de manejo para reducir estas emisiones en un experimento de campo durante un cultivo de melón (Cucumis melo L.). Los tratamientos incluyeron distintas frecuencias de riego (semanal/diario) y tipos de fertilizantes nitrogenados (urea/nitrato cálcico) aplicados por fertirriego. Fertirrigar con urea en lugar de nitrato cálcico aumentó las emisiones de N2O y NO por un factor de 2.4 y 2.9, respectivamente (P < 0.005). El riego diario redujo las emisiones de NO un 42% (P < 0.005) pero aumentó las emisiones de CO2 un 21% (P < 0.05) comparado con el riego semanal. Analizando el Poder de Calentamiento global en base al rendimiento así como los factores de emisión del NO, concluimos que el fertirriego semanal con un fertilizante de tipo nítrico es la mejor opción para combinar productividad agronómica con sostenibilidad medioambiental en este tipo de agroecosistemas. Los suelos agrícolas en las áreas semiáridas Mediterráneas se caracterizan por su bajo contenido en materia orgánica y bajos niveles de fertilidad. La aplicación de residuos de cosecha y/o abonos es una alternativa sostenible y eficiente desde el punto de vista económico para superar este problema. Sin embargo, estas prácticas podrían inducir cambios importantes en las emisiones de N2O de estos agroecosistemas, con impactos adicionales en las emisiones de CO2. En este contexto se llevó a cabo un experimento de campo durante un cultivo de cebada (Hordeum vulgare L.) bajo condiciones Mediterráneas para evaluar el efecto de combinar residuos de cosecha de maíz con distintos inputs de fertilizantes nitrogenados (purín de cerdo y/o urea) en estas emisiones. La incorporación de rastrojo de maíz incrementó las emisiones de N2O durante el periodo experimental un 105%. Sin embargo, las emisiones de NO se redujeron significativamente en las parcelas enmendadas con rastrojo. La sustitución parcial de urea por purín de cerdo redujo las emisiones netas de N2O un 46 y 39%, con y sin incorporación de residuo de cosecha respectivamente. Las emisiones netas de NO se redujeron un 38 y un 17% para estos mismos tratamientos. El ratio molar DOC:NO3 - demostró predecir consistentemente las emisiones de N2O y NO. El efecto principal de la interacción entre el fertilizante nitrogenado y el rastrojo de maíz se dio a los 4-6 meses de su aplicación, generando un aumento del N2O y una disminución del NO. La sustitución de urea por purín de cerdo puede considerarse una buena estrategia de manejo dado que el uso de este residuo orgánico redujo las emisiones de óxidos de N. Los pastos de todo el mundo proveen numerosos servicios ecosistémicos pero también suponen una importante fuente de emisión de N2O, especialmente en respuesta a la deposición de N proveniente del ganado mientras pasta. Para explorar el papel de las plantas como mediadoras de estas emisiones, se analizó si las emisiones de N2O dependen de la riqueza en especies herbáceas y/o de la composición específica de especies, en ausencia y presencia de una deposición de orina. Las hipótesis fueron: 1) las emisiones de N2O tienen una relación negativa con la productividad de las plantas; 2) mezclas de cuatro especies generan menores emisiones que monocultivos (dado que su productividad será mayor); 3) las emisiones son menores en combinaciones de especies con distinta morfología radicular y alta biomasa de raíz; y 4) la identidad de las especies clave para reducir el N2O depende de si hay orina o no. Se establecieron monocultivos y mezclas de dos y cuatro especies comunes en pastos con rasgos funcionales divergentes: Lolium perenne L. (Lp), Festuca arundinacea Schreb. (Fa), Phleum pratense L. (Php) y Poa trivialis L. (Pt), y se cuantificaron las emisiones de N2O durante 42 días. No se encontró relación entre la riqueza en especies y las emisiones de N2O. Sin embargo, estas emisiones fueron significativamente menores en ciertas combinaciones de especies. En ausencia de orina, las comunidades de plantas Fa+Php actuaron como un sumidero de N2O, mientras que los monocultivos de estas especies constituyeron una fuente de N2O. Con aplicación de orina la comunidad Lp+Pt redujo (P < 0.001) las emisiones de N2O un 44% comparado con los monocultivos de Lp. Las reducciones de N2O encontradas en ciertas combinaciones de especies pudieron explicarse por una productividad total mayor y por una complementariedad en la morfología radicular. Este estudio muestra que la composición de especies herbáceas es un componente clave que define las emisiones de N2O de los ecosistemas de pasto. La selección de combinaciones de plantas específicas en base a la deposición de N esperada puede, por lo tanto, ser clave para la mitigación de las emisiones de N2O. ABSTRACT Nitrous oxide (N2O) is a potent greenhouse gas (GHG) directly linked to applications of nitrogen (N) fertilizers to agricultural soils. Identifying mitigation strategies for these emissions based on fertilizer management without incurring in yield penalties is of economic and environmental concern. With that aim, this Thesis evaluated: (i) the use of nitrification and urease inhibitors; and (ii) interactions of N fertilizers with (1) water management, (2) crop residues and (3) plant species richness/identity. Meta-analysis, laboratory incubations, greenhouse mesocosm and field experiments were carried out in order to understand and develop effective mitigation strategies. Nitrification and urease inhibitors are proposed as means to reduce N losses, thereby increasing crop nitrogen use efficiency (NUE). However, their effect on crop yield is variable. A meta-analysis was initially conducted to evaluate their effectiveness at increasing NUE and crop productivity. Commonly used nitrification inhibitors (dicyandiamide (DCD) and 3,4-dimethylepyrazole phosphate (DMPP)) and the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) were selected for analysis as they are generally considered the best available options. Our results show that their use can be recommended in order to increase both crop yields and NUE (grand mean increase of 7.5% and 12.9%, respectively). However, their effectiveness was dependent on the environmental and management factors of the studies evaluated. Larger responses were found in coarse-textured soils, irrigated systems and/or crops receiving high nitrogen fertilizer rates. In alkaline soils (pH ≥ 8), the urease inhibitor NBPT produced the largest effect size. Given that their use represents an additional cost for farmers, understanding the best management practices to maximize their effectiveness is paramount to allow effective comparison with other practices that increase crop productivity and NUE. Based on the meta-analysis results, NBPT was identified as a mitigation option with large potential. Urease inhibitors (UIs) have shown to promote high N use efficiency by reducing ammonia (NH3) volatilization. In the last few years, however, some field researches have shown an effective mitigation of UIs over N2O losses from fertilized soils under conditions of low soil moisture. Given the inherent high variability of field experiments where soil moisture content changes rapidly, it has been impossible to mechanistically understand the potential of UIs to reduce N2O emissions and its dependency on the soil water-filled pore space (WFPS). An incubation experiment was carried out aiming to assess what is the main biotic mechanism behind N2O emission when UIs are applied under different soil moisture conditions (40, 60 and 80% WFPS), and to analyze to what extent the soil WFPS regulates the effect of the inhibitor over N2O emissions. A second UI (i.e. PPDA) was also used aiming to compare the effect of NBPT with that of another commercially available urease inhibitor; this allowed us to see if the effect of NBPT was inhibitor-specific or not. The N2O emissions at 40% WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80% WFPS. Compared to urea alone, NBPT+U reduced the N2O emissions at 60% WFPS but had no effect at 80% WFPS. The application of PPDA significantly increased the emissions with respect to U at 80% WFPS whereas no significant effect was found at 60% WFPS. At 80% WFPS denitrification was the main source of N2O emissions for all treatments. Both nitrification and denitrification had a determinant role on these emissions at 60% WFPS. These results suggest that adequate management of the UI NBPT can provide, under certain soil conditions, an opportunity for N2O mitigation. We translated our previous results to realistic field conditions by means of a field experiment with a barley crop (Hordeum vulgare L.) under rainfed Mediterranean conditions in which we evaluated the effectiveness of NBPT to reduce N losses and increase crop yields. Crop yield, soil mineral N concentrations, dissolved organic carbon (DOC), denitrification potential, NH3, N2O and nitric oxide (NO) fluxes were measured during the growing season. The inclusion of the inhibitor reduced NH3 emissions in the 30 d following urea application by 58% and net N2O and NO emissions in the 95 d following urea application by 86 and 88%, respectively. NBPT addition also increased grain yield by 5% and N uptake by 6%, although neither increase was statistically significant. Under the experimental conditions presented here, these results demonstrate the potential of the urease inhibitor NBPT in abating NH3, N2O and NO emissions from arable soils fertilized with urea, slowing urea hydrolysis and releasing lower concentrations of NH4 + to the upper soil layer. Drip irrigation combined with split application of N fertilizer dissolved in the irrigation water (i.e. drip fertigation) is commonly considered best management practice for water and nutrient efficiency. Some of the main factors (WFPS, NH4 + and NO3 -) regulating the emissions of GHGs (i.e. N2O, carbon dioxide (CO2) and methane (CH4)) and NO can easily be manipulated by drip fertigation without yield penalties. In this study, we tested management options to reduce these emissions in a field experiment with a melon (Cucumis melo L.) crop. Treatments included drip irrigation frequency (weekly/daily) and type of N fertilizer (urea/calcium nitrate) applied by fertigation. Crop yield, environmental parameters, soil mineral N concentrations, N2O, NO, CH4, and CO2 fluxes were measured during the growing season. Fertigation with urea instead of calcium nitrate increased N2O and NO emissions by a factor of 2.4 and 2.9, respectively (P < 0.005). Daily irrigation reduced NO emissions by 42% (P < 0.005) but increased CO2 emissions by 21% (P < 0.05) compared with weekly irrigation. Based on yield-scaled Global Warming Potential as well as NO emission factors, we conclude that weekly fertigation with a NO3 --based fertilizer is the best option to combine agronomic productivity with environmental sustainability. Agricultural soils in semiarid Mediterranean areas are characterized by low organic matter contents and low fertility levels. Application of crop residues and/or manures as amendments is a cost-effective and sustainable alternative to overcome this problem. However, these management practices may induce important changes in the nitrogen oxide emissions from these agroecosystems, with additional impacts on CO2 emissions. In this context, a field experiment was carried out with a barley (Hordeum vulgare L.) crop under Mediterranean conditions to evaluate the effect of combining maize (Zea mays L.) residues and N fertilizer inputs (organic and/or mineral) on these emissions. Crop yield and N uptake, soil mineral N concentrations, dissolved organic carbon (DOC), denitrification capacity, N2O, NO and CO2 fluxes were measured during the growing season. The incorporation of maize stover increased N2O emissions during the experimental period by c. 105 %. Conversely, NO emissions were significantly reduced in the plots amended with crop residues. The partial substitution of urea by pig slurry reduced net N2O emissions by 46 and 39 %, with and without the incorporation of crop residues respectively. Net emissions of NO were reduced 38 and 17 % for the same treatments. Molar DOC:NO3 - ratio was found to be a robust predictor of N2O and NO fluxes. The main effect of the interaction between crop residue and N fertilizer application occurred in the medium term (4-6 month after application), enhancing N2O emissions and decreasing NO emissions as consequence of residue incorporation. The substitution of urea by pig slurry can be considered a good management strategy since N2O and NO emissions were reduced by the use of the organic residue. Grassland ecosystems worldwide provide many important ecosystem services but they also function as a major source of N2O, especially in response to N deposition by grazing animals. In order to explore the role of plants as mediators of these emissions, we tested whether and how N2O emissions are dependent on grass species richness and/or specific grass species composition in the absence and presence of urine deposition. We hypothesized that: 1) N2O emissions relate negatively to plant productivity; 2) four-species mixtures have lower emissions than monocultures (as they are expected to be more productive); 3) emissions are lowest in combinations of species with diverging root morphology and high root biomass; and 4) the identity of the key species that reduce N2O emissions is dependent on urine deposition. We established monocultures and two- and four-species mixtures of common grass species with diverging functional traits: Lolium perenne L. (Lp), Festuca arundinacea Schreb. (Fa), Phleum pratense L. (Php) and Poa trivialis L. (Pt), and quantified N2O emissions for 42 days. We found no relation between plant species richness and N2O emissions. However, N2O emissions were significantly reduced in specific plant species combinations. In the absence of urine, plant communities of Fa+Php acted as a sink for N2O, whereas the monocultures of these species constituted a N2O source. With urine application Lp+Pt plant communities reduced (P < 0.001) N2O emissions by 44% compared to monocultures of Lp. Reductions in N2O emissions by species mixtures could be explained by total biomass productivity and by complementarity in root morphology. Our study shows that plant species composition is a key component underlying N2O emissions from grassland ecosystems. Selection of specific grass species combinations in the context of the expected nitrogen deposition regimes may therefore provide a key management practice for mitigation of N2O emissions.

Ranking factors affecting emissions of GHG from incubated agricultural soils

Agriculture significantly contributes to global greenhouse gas (GHG) missions and there is a need to develop effective mitigation strategies. The efficacy of methods to reduce GHG fluxes from agricultural soils can be affected by a range of interacting management and environmental factors. Uniquely, we used the Taguchi experimental design methodology to rank the relative importance of six factors known to affect the emission of GHG from soil: nitrate (NO3?) addition, carbon quality (labile and non-labile C), soil temperature, water-filled pore space (WFPS) and extent of soil compaction. Grassland soil was incubated in jars where selected factors, considered at two or three amounts within the experimental range, were combined in an orthogonal array to determine the importance and interactions between factors with a L16 design, comprising 16 experimental units. Within this L16 design, 216 combinations of the full factorial experimental design were represented. Headspace nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations were measured and used to calculate fluxes. Results found for the relative influence of factors (WFPS and NO3? addition were the main factors affecting N2O fluxes, whilst glucose, NO3? and soil temperature were the main factors affecting CO2 and CH4 fluxes) were consistent with those already well documented. Interactions between factors were also studied and results showed that factors with Little individual influence became more influential in combination. The proposed methodology offers new possibilities for GHG researchers to study interactions between influential factors and address the optimized sets of conditions to reduce GHG emissions in agro-ecosystems, while reducing the number of experimental units required compared with conventional experimental procedures that adjust one variable at a time.

Do cover crops enhance N2O, CO2 or CH4 emissions from soil in Mediterranean arable systems?

This study evaluates the effect of planting three cover crops (CCs) (barley, Hordeum vulgare L.; vetch, Vicia villosa L.; rape, Brassica napus L.) on the direct emission of N2O, CO2 and CH4 in the intercrop period and the impact of incorporating these CCs on the emission of greenhouse gas (GHG) from the forthcoming irrigated maize (Zea mays L.) crop. Vetch and barley were the CCs with the highest N2O and CO2 losses (75 and 47% increase compared with the control, respectively) in the fallow period. In all cases, fluxes of N2O were increased through N fertilization and the incorporation of barley and rape residues (40 and 17% increase, respectively). The combination of a high C:N ratio with the addition of an external source of mineral N increased the fluxes of N2O compared with − Ba and − Rp. The direct emissions of N2O were lower than expected for a fertilized crop (0.10% emission factor, EF) compared with other studies and the IPCC EF. These results are believed to be associated with a decreased NO3− pool due to highly denitrifying conditions and increased drainage. The fluxes of CO2 were in the range of other fertilized crops (i.e., 1118.71–1736.52 kg CO2–C ha− 1). The incorporation of CC residues enhanced soil respiration in the range of 21–28% for barley and rape although no significant differences between treatments were detected. Negative CH4 fluxes were measured and displayed an overall sink effect for all incorporated CC (mean values of − 0.12 and − 0.10 kg CH4–C ha− 1 for plots with and without incorporated CCs, respectively).

Management of irrigation frequency and nitrogen fertilization to mitigate GHG and NO emissions from drip-fertigated crops

Drip irrigation combined with split application of fertilizer nitrogen (N) dissolved in the irrigation water (i.e. drip fertigation) is commonly considered best management practice for water and nutrient efficiency. As a consequence, its use is becoming widespread. Some of the main factors (water-filled pore space, NH4+ and NO3−) regulating the emissions of greenhouse gases (i.e. N2O, CO2 and CH4) and NO from agroecosystems can easily be manipulated by drip fertigation without yield penalties. In this study, we tested management options to reduce these emissions in a field experiment with a melon (Cucumis melo L.) crop. Treatments included drip irrigation frequency (weekly/daily) and type of N fertilizer (urea/calcium nitrate) applied by fertigation. Crop yield, environmental parameters, soil mineral N concentrations and fluxes of N2O, NO, CH4 and CO2 were measured during 85 days. Fertigation with urea instead of calcium nitrate increased N2O and NO emissions by a factor of 2.4 and 2.9, respectively (P < 0.005). Daily irrigation reduced NO emissions by 42% (P < 0.005) but increased CO2 emissions by 21% (P < 0.05) compared with weekly irrigation. We found no relation between irrigation frequency and N2O emissions. Based on yield-scaled Global Warming Potential as well as NO cumulative emissions, we conclude that weekly fertigation with a NO3−-based fertilizer is the best option to combine agronomic productivity with environmental sustainability. Our study shows that adequate management of drip fertigation, while contributing to the attainment of water and food security, may provide an opportunity for climate change mitigation.

Efficiency and environmental indexes to evaluate the sustainability of mineral and organic fertilization in an irrigated melon crop

Melon is traditionally cultivated in fertigated farmlands in the center of Spain with high inputs of water and N fertilizer. Excess N can have a negative impact, from the economic point of view, since it can diminish the production and quality of the fruit, from the environmental point of view, since it is a very mobile element in the soil and can contaminate groundwater. From health point of view, nitrate can be accumulated in fruit pulp, and, in addition, groundwater is the fundamental supply source of human populations. Best management practices are particularly necessary in this region as many zones have been declared vulnerable to NO3- pollution (Directive 91/676/CEE) During successive years, a melon crop (Cucumis melo L.) was grown under field conditions applying mineral and organic fertilizers under drip irrigation. Different doses of ammonium nitrate were used as well as compost derived from the wine-distillery industry which is relevant in this area. The present study reviews the most common N efficiency indexes under the different management options with a view to maximizing yield and minimizing N loss.

Estudio de la influencia de la relación C/N en la desnitrificación y metanogénesis de aguas residuales en un reactor anaeróbico de lecho fluidizado inverso

La nitrificación-desnitrificación es el proceso biológico tradicional para la remoción de nitrógeno de las aguas residuales (Ruiz G. et al., 2006a), siendo fundamental ya que contribuye a controlar la eutroficación de los cuerpos receptores. Debido al deterioro que sobre la disponibilidad de los recursos han ejercido las actividades antropogénicas, es necesario orientar el tratamiento de las aguas residuales hacia tecnologías que ofrezcan el mayor grado de sustentabilidad, planteando innovaciones en el tratamiento. El presente proyecto de tesis doctoral versa sobre el estudio de la influencia de la relación C/N en la desnitrificación y metanogénesis de aguas residuales urbanas en un reactor anaeróbico de lecho fluidizado inverso (RLFI). Previamente a la realización de las pruebas experimentales de variación de la relación C/N, se llevó a cabo la etapa de arranque del RLFI la cual se inició en modo batch, favoreciendo la formación y adhesión de biopelícula al medio de soporte utilizado (Extendosphere). Después, sobrevino la operación en modo continuo desde una carga volumétrica aplicada (CVA) de 0.5 g DQOs/L⋅d hasta alcanzar 4 g DQOs/L⋅d, carga volumétrica a la cual se logró la plena estabilización del reactor, siendo la alta variabilidad de la concentración de DQOs en el agua residual urbana de alimentación, la principal problemática que ocasionó retrasos en la estabilidad del reactor. A una CVA de 4 g DQOs/L⋅d en estado estacionario, el valor mínimo de eficiencia de remoción de DQOs fue del 32.36% y el máximo de 66.99%. En estas condiciones el porcentaje de metano presente en el biogás producido tuvo un valor medio de 85.57 ± 2.93%, siendo un valor alto comparado con otros porcentajes de metano encontrados en la digestión anaerobia de aguas residuales urbanas. El YCH4 tuvo un valor medio de 0.316 ± 0.110 LCH4/g DQOrem⋅día. Los porcentajes de metanización variaron en el rango de 20.50 a 100%, registrándose un valor medio de 73.42 ± 25.63%. La considerable variabilidad en el porcentaje de metanización se debió principalmente a que se presentaron eventos de lavado de soporte colonizado, lo cual propició que las actividades metabólicas fueran orientadas hacia formación de biopelícula (anabolismo) en vez de estar dirigidas hacia producción de metano (catabolismo). En relación a los ensayos con variación de la relación C/N, se manejaron relaciones DQOs/N-NO3 en el rango de 1.65 a 21.1 g DQOs/g N-NO3. La tasa de remoción anaerobia de DQOs se incrementó con la concentración de sustrato en una relación casi lineal, ajustándose a una cinética de primer orden, lo que regularmente se presenta a concentraciones bajas de sustrato. La eficiencia del proceso de desnitrificación fue por lo regular alta, incrementándose ligeramente con la concentración de DQOs en el influente, con valores en el rango de 73.8 a 99.1%. Por otra parte, la tasa de remoción por metanogénesis se incrementó con la concentración relativa de sustrato (es decir, a mayores relaciones DQOs/N-NO3), siendo más sensitiva la metanogénesis a la concentración relativa de sustrato que la desnitrificación. Conforme aumentó la relación DQOs/N-NO3, la desnitrificación, de ser la ruta metabólica principal de utilización de la materia orgánica (comparada con la metanización), empezó a combinarse con la metanización. De manera evidente, a las relaciones DQOs/N-NO3 probadas, se manifestaron más las actividades desnitrificantes, quedando reflejadas por el alto porcentaje de utilización de la DQOs removida hacia la desnitrificación. La relación experimental DQOs/N-NO3 a la cual se pudiera haber cumplido con el requerimiento de materia orgánica (en términos de DQOs) para la desnitrificación de nitratos en las aguas residuales urbanas tratadas resultó aproximadamente ser igual a 7.1 g DQOs/g N-NO3. A una CVA de 4 g DQOs/L⋅d, se obtuvo un diámetro promedio máximo de soporte colonizado igual a 266.106 ± 69.279 μm aunque, hay que indicarlo, se presentaron fluctuaciones, las cuales se reflejaron también en el espesor de la biopelícula, el cual tuvo un valor máximo de 50.099 μm y un valor promedio de 37.294 ± 11.199 μm. Estas fluctuaciones pudieron deberse a la existencia de corrientes preferenciales dentro del reactor, las cuales no permitieron un acceso equitativo del sustrato a todo el lecho. Nitrification-denitrification is the traditional biological process for nitrogen removal from wastewaters (Ruiz G. et al., 2006a), being fundamental since it contributes to control the eutrophication of the receiving waters. Due to the deterioration that on the availability of the aquatic resources the anthropogenic activities have exerted, it is necessary to orient the treatment of wastewaters towards technologies that offer the greater degree of sustainability, raising innovations in the treatment. This work studied the influence of C/N ratio on denitrification and methanogenesis of urban wastewaters in an inverse fluidized bed reactor (IFBR). Previously to the accomplishment of the experimental tests with variation of C/N ratio, the start up of the IFBR was carried out in batch way, encouraging the formation and adhesion of biofilm to Extendosphere, which it was used as support. The operation in continuous way carried out from an organic loading rate (OLR) of 0.5 g CODs/L ∙ d to 4 g CODs/L ∙ d, when the steady-state was reached. The high variability of the CODs of the urban wastewaters caused delays in the stability of the reactor. Once stationary state was reached, the removal efficiency of CODs ranged from 32.36 to 66.99% to 4 g CODs/L ∙ d. In these conditions the percentage of methane in produced biogas had an average value of 85.57 ± 2.93%, being a high value compared with other studies treating anaerobically urban wastewaters. The YCH4 had an average value of 0.316 ± 0.110 LCH4/g CODrem ∙ d. The percentage of methanisation ranged from 20.50 to 100%, with an average value of 73.42 ± 25.63%. The considerable variability in the methanisation percentage occurred mainly due events of wash-out of colonized support, which caused that the metabolic activities were oriented towards formation of biofilm (anabolism) instead of methane production (catabolism). Concerning the tests with variation of C/N ratio, CODs/NO3-N ratios from 1.65 to 21.1 g CODs/g NO3-N were proved. The CODs anaerobic removal rate increased with the substrate concentration in an almost linear relation, adjusting to a kinetic of first order, which regularly appears to low concentrations of substrate. Efficiency of the denitrification process was regularly high, and it increased slightly with the CODs concentration in the influent, ranging from 73.8 to 99.1%. On the other hand, the CODs removal rate by methanogenesis increased with the substrate relative concentration (e.g., to greater CODs/NO3-N ratios), being more sensitive the methanogenesis to the substrate relative concentration that the denitrification. When the CODs/NO3-N ratio increased, the denitrification, of being the main metabolic route of use of the organic matter (compared with the methanogenesis), began to be combined with the methanogenesis. Definitively, to the proven CODs/NO3-N ratios the denitrification processes were more pronounced, being reflected by the high percentage of use of the removed CODs towards denitrification. The experimental CODs/NO3-N ratio to which it was possible to have been fulfilled the requirement of organic matter (in terms of CODs) for the denitrification of nitrates in urban wastewaters turned out to be approximately 7.1 g CODs/g NO3-N. It was obtained a maximum average diameter of colonized support of 266.106 ± 69.279 μm to 4 g CODs/L ∙ d, although it is necessary to indicate that appeared fluctuations in the thickness of biofilm, which had a maximum value of 50.099 μm and an average value of 37.294 ± 11.199 μm. These fluctuations could be due to the existence of preferential currents within the reactor, which did not allow an equitable access of the substrate to all the bed.

Modeling GHG emissions, N and C dynamics in Spanish agricultural soils.

To date, only few initiatives have been carried out in Spain in order to use mathematical models (e.g. DNDC, DayCent, FASSET y SIMSNIC) to estimate nitrogen (N) and carbon (C) dynamics as well as greenhouse gases (GHG) in Spanish agrosystems. Modeling at this level may allow to gain insight on both the complex relationships between biological and physicochemical processes, controlling the processes leading to GHG production and consumption in soils (e.g. nitrification, denitrification, decomposing, etc.), and the interactions between C and N cycles within the different components of the continuum plant-soil-environment. Additionally, these models can simulate the processes behind production, consumition and transport of GHG (e.g. nitrous oxide, N2O, and carbon dioxide, CO2) in the short and medium term and at different scales. Other sources of potential pollution from soils can be identified and quantified using these process-based models (e.g. NO3 y NH3).

Water and nitrogen footprint in an irrigated crop under mineral and organic fertilization

In order to establish rational nitrogen (N) application and reduce groundwater contamination, a clearer understanding of the N distribution through the growing season and its balance is crucial. Excessive doses of N and/or water applied to fertigated crops involve a substantial risk of aquifer contamination by nitrate; but knowledge of N cycling and availability within the soil could assist in avoiding this excess. In central Spain, the main horticultural fertigated crop is the melon type ?piel de sapo¿ and it is cultivated in vulnerable zones to nitrate pollution (Directive 91/676/CEE). However, until few years ago there were not antecedents related to the optimization of nitrogen fertilization together with irrigation. Water and N footprint are indicators that allow assessing the impact generated by different agricultural practices, so they can be used to improve the management strategies in fertigated crop systems. The water footprint distinguishes between blue water (sources of water applied to the crop, like irrigation and precipitation), green water (water used by the crop and stored in the soil), and it is furthermore possible to quantify the impact of pollution by calculating the grey water, which is defined as the volume of polluted water created from the growing and production of crops. On the other hand, the N footprint considers green N (nitrogen consumed by the crops and stored in the soil), blue N (N available for crop, like N applied with mineral and/or organic fertilizers, N applied with irrigation water and N mineralized during the crop period), whereas grey N is the amount of N-NO3- washed from the soil to the aquifer. All these components are expressed as the ratio between the components of water or N footprint and the yield (m3 t-1 or kg N t-1 respectively). The objetives of this work were to evaluate the impact derivated from the use of different fertilizer practices in a melon crop using water and N footprint.