Propuesta metodológica para el análisis y protección de la calidad del agua subterránea de acuerdo con los requerimientos de la Directiva Marco y la Directiva derivada de Aguas Subterráneas

La protección de las aguas subterráneas es una prioridad de la política medioambiental de la UE. Por ello ha establecido un marco de prevención y control de la contaminación, que incluye provisiones para evaluar el estado químico de las aguas y reducir la presencia de contaminantes en ellas. Las herramientas fundamentales para el desarrollo de dichas políticas son la Directiva Marco del Agua y la Directiva Hija de Aguas Subterráneas. Según ellas, las aguas se consideran en buen estado químico si: • la concentración medida o prevista de nitratos no supera los 50 mg/l y la de ingredientes activos de plaguicidas, de sus metabolitos y de los productos de reacción no supera el 0,1 μg/l (0,5 μg/l para el total de los plaguicidas medidos) • la concentración de determinadas sustancias de riesgo es inferior al valor umbral fijado por los Estados miembros; se trata, como mínimo, del amonio, arsénico, cadmio, cloruro, plomo, mercurio, sulfatos, tricloroetileno y tetracloroetileno • la concentración de cualquier otro contaminante se ajusta a la definición de buen estado químico enunciada en el anexo V de la Directiva marco sobre la política de aguas • en caso de superarse el valor correspondiente a una norma de calidad o a un valor umbral, una investigación confirma, entre otros puntos, la falta de riesgo significativo para el medio ambiente. Analizar el comportamiento estadístico de los datos procedentes de la red de seguimiento y control puede resultar considerablemente complejo, debido al sesgo positivo que suelen presentar dichos datos y a su distribución asimétrica, debido a la existencia de valores anómalos y diferentes tipos de suelos y mezclas de contaminantes. Además, la distribución de determinados componentes en el agua subterránea puede presentar concentraciones por debajo del límite de detección o no ser estacionaria debida a la existencia de tendencias lineales o estacionales. En el primer caso es necesario realizar estimaciones de esos valores desconocidos, mediante procedimientos que varían en función del porcentaje de valores por debajo del límite de detección y el número de límites de detección aplicables. En el segundo caso es necesario eliminar las tendencias de forma previa a la realización de contrastes de hipótesis sobre los residuos. Con esta tesis se ha pretendido establecer las bases estadísticas para el análisis riguroso de los datos de las redes de calidad con objeto de realizar la evaluación del estado químico de las masas de agua subterránea para la determinación de tendencias al aumento en la concentración de contaminantes y para la detección de empeoramientos significativos, tanto en los casos que se ha fijado un estándar de calidad por el organismo medioambiental competente como en aquéllos que no ha sido así. Para diseñar una metodología que permita contemplar la variedad de casos existentes, se han analizado los datos de la Red Oficial de Seguimiento y Control del Estado Químico de las Aguas Subterráneas del Ministerio de Agricultura, Alimentación y Medio Ambiente (Magrama). A continuación, y dado que los Planes Hidrológicos de Cuenca son la herramienta básica de las Directivas, se ha seleccionado la Cuenca del Júcar, dada su designación como cuenca piloto en la estrategia de implementación común (CIS) de la Comisión Europea. El objetivo principal de los grupos de trabajo creados para ello se dirigió a implementar la Directiva Derivada de Agua Subterráneas y los elementos de la Directiva Marco del Agua relacionadas, en especial la toma de datos en los puntos de control y la preparación del primer Plan de Gestión de Cuencas Hidrográficas. Dada la extensión de la zona y con objeto de analizar una masa de agua subterránea (definida como la unidad de gestión en las Directivas), se ha seleccionado una zona piloto (Plana de Vinaroz Peñiscola) en la que se han aplicado los procedimientos desarrollados con objeto de determinar el estado químico de dicha masa. Los datos examinados no contienen en general valores de concentración de contaminantes asociados a fuentes puntuales, por lo que para la realización del estudio se han seleccionado valores de concentración de los datos más comunes, es decir, nitratos y cloruros. La estrategia diseñada combina el análisis de tendencias con la elaboración de intervalos de confianza cuando existe un estándar de calidad e intervalos de predicción cuando no existe o se ha superado dicho estándar. De forma análoga se ha procedido en el caso de los valores por debajo del límite de detección, tomando los valores disponibles en la zona piloto de la Plana de Sagunto y simulando diferentes grados de censura con objeto de comparar los resultados obtenidos con los intervalos producidos de los datos reales y verificar de esta forma la eficacia del método. El resultado final es una metodología general que integra los casos existentes y permite definir el estado químico de una masa de agua subterránea, verificar la existencia de impactos significativos en la calidad del agua subterránea y evaluar la efectividad de los planes de medidas adoptados en el marco del Plan Hidrológico de Cuenca. ABSTRACT Groundwater protection is a priority of the EU environmental policy. As a result, it has established a framework for prevention and control of pollution, which includes provisions for assessing the chemical status of waters and reducing the presence of contaminants in it. The measures include: • criteria for assessing the chemical status of groundwater bodies • criteria for identifying significant upward trends and sustained concentrations of contaminants and define starting points for reversal of such trends • preventing and limiting indirect discharges of pollutants as a result of percolation through soil or subsoil. The basic tools for the development of such policies are the Water Framework Directive and Groundwater Daughter Directive. According to them, the groundwater bodies are considered in good status if: • measured or predicted concentration of nitrate does not exceed 50 mg / l and the active ingredients of pesticides, their metabolites and reaction products do not exceed 0.1 mg / l (0.5 mg / l for total of pesticides measured) • the concentration of certain hazardous substances is below the threshold set by the Member States concerned, at least, of ammonium, arsenic, cadmium, chloride, lead, mercury, sulphates, trichloroethylene and tetrachlorethylene • the concentration of other contaminants fits the definition of good chemical status set out in Annex V of the Framework Directive on water policy • If the value corresponding to a quality standard or a threshold value is exceeded, an investigation confirms, among other things, the lack of significant risk to the environment. Analyzing the statistical behaviour of the data from the monitoring networks may be considerably complex due to the positive bias which often presents such information and its asymmetrical distribution, due to the existence of outliers and different soil types and mixtures of pollutants. Furthermore, the distribution of certain components in groundwater may have concentrations below the detection limit or may not be stationary due to the existence of linear or seasonal trends. In the first case it is necessary to estimate these unknown values, through procedures that vary according to the percentage of values below the limit of detection and the number of applicable limits of detection. In the second case removing trends is needed before conducting hypothesis tests on residuals. This PhD thesis has intended to establish the statistical basis for the rigorous analysis of data quality networks in order to conduct the evaluation of the chemical status of groundwater bodies for determining upward and sustained trends in pollutant concentrations and for the detection of significant deterioration in cases in which an environmental standard has been set by the relevant environmental agency and those that have not. Aiming to design a comprehensive methodology to include the whole range of cases, data from the Groundwater Official Monitoring and Control Network of the Ministry of Agriculture, Food and Environment (Magrama) have been analysed. Then, since River Basin Management Plans are the basic tool of the Directives, the Júcar river Basin has been selected. The main reason is its designation as a pilot basin in the common implementation strategy (CIS) of the European Commission. The main objective of the ad hoc working groups is to implement the Daughter Ground Water Directive and elements of the Water Framework Directive related to groundwater, especially the data collection at control stations and the preparation of the first River Basin Management Plan. Given the size of the area and in order to analyze a groundwater body (defined as the management unit in the Directives), Plana de Vinaroz Peñíscola has been selected as pilot area. Procedures developed to determine the chemical status of that body have been then applied. The data examined do not generally contain pollutant concentration values associated with point sources, so for the study concentration values of the most common data, i.e., nitrates and chlorides have been selected. The designed strategy combines trend analysis with the development of confidence intervals when there is a standard of quality and prediction intervals when there is not or the standard has been exceeded. Similarly we have proceeded in the case of values below the detection limit, taking the available values in Plana de Sagunto pilot area and simulating different degrees of censoring in order to compare the results obtained with the intervals achieved from the actual data and verify in this way the effectiveness of the method. The end result is a general methodology that integrates existing cases to define the chemical status of a groundwater body, verify the existence of significant impacts on groundwater quality and evaluate the effectiveness of the action plans adopted in the framework of the River Basin Management Plan.

Effects of water potential on spore germination and viability of Fusarium species

Germination of macroconidia and/or microconidia of 24 strains of Fusarium solani, F. chlamydosporum, F. culmorum, F. equiseti, F. verticillioides, F. sambucinum, F. oxysporum and F. proliferatum isolated from fluvial channels and sea beds of the south-eastern coast of Spain, and three control strains (F. oxysporum isolated from affected cultures) was studied in distilled water in response to a range of water potentials adjusted with NaCI. (0, -13.79, -41.79, -70.37, -99.56 and -144.54 bars). The vialibility (UFC/ml) of suspension was also tested in three time periods (0,24 and 48h). Conidia always germinated in distilled water. The pattern of conidial germination obseved of F. verticillioides, F. oxysporum, F. proliferatum, F. chlamydosporum and F. culmorum was similar. A great diminution of spore germination was found in -13.79 bars solutions. Spore germination percentage for F. solani isolates was maximal at 48 h. and -13.79 bars with 21.33% spore germination, 16% higher than germination in distilled water. F. equiseti shows the maximum germination percentage in -144.54 bars solution in 24 h time with 12.36% germination. These results did not agree with those obtained in the viability test where maximum germination was found in distilled water. The viability analysis showed the great capacity of F. verticilloides strains to form viable colonies, even in such extreme conditions as -144,54 bars after 24 h F. proliferatum colony formation was prevented in the range of -70.37 bars. These results show the clear affectation of water potential to conidia germination of Fusaria. The ability of certain species of Fusarium to develop a saprophytic life in the salt water of the Mediterraneam Sea could be certain. Successful germination, even under high salty media conditions, suggests taht Fusarium spp. could have a competitive advantage over other soil fungi in crops irrigated with saline water. In the specific case of F. solani, water potential of -13.79 bars affected germination positively. It could indicate that F. solani has an special physiological mechanism of survival in low water potential environments.

Species of Fusarium isolated from river and sea water of Southeastern Spain and pathogenicity on four plant species

Species of Fusarium were isolated from water samples collected from the Andarax River and coastal sea water of the Mediterranean in Granada and Almería provinces of southeastern Spain. In total, 18 water samples were analyzed from the Andarax River, and 10 species of Fusarium were isolated: Fusarium anthophilum, F. acuminatum, F. chlamydosporum, F. culmorum, F. equiseti, F. verticillioides, F. oxysporum, F. proliferatum, F. solani, and F. solani. When considering the samples by their origins, 77.8% of the river water samples yielded at least one species of Fusarium , with F. oxysporum comprising 72.2% of the total isolates. In the case of marine water, 45.5% of the samples yielded at least one species of Fusarium, with F. solani comprising 36.3% of the total isolates. The pathogenicity of 41 isolates representing nine of the species collected from river an sea water during the study ws evluated on barley, kohlrabe, melon, and tomato. Inoculation with F. acuminatum, F. chlamydosporum, F. culmorum, F. equiseti, F. verticillioides, F. oxysporum, F. proliferatum F. solani, and F. sambucinum resulted in pre-and post-emergence damping off. Pathogenicity of Fusarium isolates did not seem to be related to the origin of the isolates (sea water or fresh water). However, the presence of pathogenic species of Fusarium in river water flowing to the sea could indicate long-distance dispersal in natural water environments

Limiting properties in the characterisation of mixed recycled aggregates for use in the manufacture of concrete

El objetivo principal de este trabajo de investigación es estudiar las propiedades del árido reciclado mixto para la fabricación de hormigón reciclado en aplicaciones no estructurales. Se ha realizado la caracterización completa de 35 muestras de áridos reciclados mixtos gruesos de distinta calidad, procedentes de 13 plantas de tratamiento diferentes de la geografía española. Se han estudiado las correlaciones que existen entre las diferentes propiedades, en particular, con la absorción de agua, el contenido de sulfatos y la composición. Se propone una clasificación de los áridos reciclados y se limita de forma indicativa el contenido de yeso para que una muestra de árido reciclado mixto cumpla con la limitación del 0,8% de los sulfatos solubles en ácido de la Instrucción EHE-08. Recycling of construction and demolition waste (CDW) has become a widespread concern in Spain for the last years, as a way to preserve natural resources and achieve a better control of waste disposal sites.Specific applications which make use of mixed recycled aggregates are of great importance, as this types of aggregates constitute the majority of the total production. Structural and non-structural concrete is one of the possible applications, being this the main goal of our study. This paper presents a study on the physical and chemical characteristics of mixed recycled aggregates which have been obtained from different CDW treatment plants of Spain. Correlations between the different properties were investigated in order to find criterions of acceptance for recycled aggregates to be used in concrete. The comparison between the properties offers the possibility of pre-selecting a great quantity of mixed recycled aggregates, these being suitable for either structural and non-structural concrete. The determination of water absorption and the gypsum content are good indicators in order to evaluate the quality of the mixed recycled aggregates for its application in the production of concrete.

Estudio de hormigones reciclados no estructurales fabricados con árido reciclado mixto : propiedades mecánicas y expansión debida al contenido de sulfatos

El objetivo principal de este trabajo de investigación es estudiar las posibilidades de utilización del árido reciclado mixto para un hormigón reciclado en aplicaciones no estructurales, justificando mediante la experimentación la validez para esta aplicación, tanto del árido reciclado como del hormigón reciclado. Esta tesis se centró en los aspectos más restrictivos y limitativos en la utilización de los áridos mixtos en hormigón reciclado, basándose tanto en la normativa internacional existente como en los resultados obtenidos en los estudios bibliográficos consultados. La primera tarea realizada fue la caracterización completa de las propiedades del árido reciclado mixto, recogiendo especialmente los siguientes aspectos: granulometría, contenido de finos, absorción y densidades, composición del árido reciclado, índice de lajas, coeficiente de Los Ángeles, partículas ligeras y contenido de sulfatos. De este estudio de los áridos reciclados, se han destacado relaciones entre las propiedades. Las diferentes correlaciones permiten proponer criterios de calidad de un árido reciclado mixto para un hormigón reciclado. Se ha elegido un árido reciclado mixto entre los estudiados, de características límite admisibles, para obtener resultados conservadores sobre el hormigón reciclado fabricado con él. En una segunda etapa, se ha realizado un estudio de dosificación completo del hormigón reciclado, evaluando la consistencia del hormigón en estado fresco y la resistencia a compresión del hormigón en estado endurecido y se ha comparado con las mismas propiedades de un hormigón convencional. Se ha analizado la capacidad de absorción del árido conseguida con los métodos de presaturación empleados y en función de su estado de humedad, para poder evaluar las relaciones agua/cemento totales y efectivas del hormigón. Se ha estudiado el efecto de estos dos parámetros tanto en la consistencia como en la resistencia del hormigón reciclado. Finalmente, se ha estudiado el hormigón fabricado con un 50% y 100% de una partida de árido reciclado mixto de calidad admisible y se han ensayado las siguientes propiedades: consistencia, resistencia a compresión, resistencia a tracción indirecta, módulo de elasticidad dinámico, cambios de longitud, porosidad abierta y microscopía. Para analizar el efecto de los sulfatos, se han añadido artificialmente cantidades de yeso controladas en el hormigón reciclado. Se fabricaron hormigones con dos tipos de cemento, un cemento CEM I 42,5 R con elevado contenido de C3A, que debería dar lugar a expansiones mayores y un cemento con adiciones puzolánicas CEM II A-P 42,5 R, que atenuaría el comportamiento expansivo en el hormigón. Los resultados finales indican que la utilización del árido reciclado mixto en proporciones de hasta un 50%, permiten cubrir la gama de resistencias más exigentes dentro del hormigón no estructural. El contenido de sulfatos puede variar desde un 0,8% hasta un 1,9%, según el tipo de cemento y la proporción de sustitución del árido natural por árido reciclado mixto. Tanto en el caso del árido reciclado como en el hormigón, se ha realizado un estudio comparativo entre el conjunto de datos recopilados en la bibliografía y los obtenidos en este estudio experimental. En varias propiedades del hormigón reciclado, se han comparado los resultados con las fórmulas de la Instrucción EHE-08, para establecer unos coeficientes de corrección a aplicar a un hormigón reciclado con fines no estructurales. The main objective of this investigation work is to study the possibilities of using recycled mixed aggregate for a recycled concrete in non structural applications, justifying by means of experimentation both the validity of the recycled aggregate and recycled concrete. This thesis focused on the most restrictive and limiting aspects in the mixed aggregate use in recycled concrete, on the basis of the international standards as well on the results obtained in the bibliographic studies consulted. The first task achieved was the complete charcaterization of the mixed recycled aggregate properties, specially the following aspects: grain size analysis, fines content, absorption and densities, recycled aggregate composition, flakiness index, Los Angeles coefficient, lightweight particles and sulphate content. From this study, correlations between the properties were highlighted. The different correlations make possible to propose quality criterions for recycled mixed aggregate in concrete. Among the recycled aggregates studied, one of acceptable characteristics but near the limits established, was chosen to obtain conservative results in the recycled concrete made with it. In a second step, a complete recycled concrete mix design was made, to evaluate concrete consistency in the fresh state and concrete compressive strength in the hardened state and its properties were compared to those of a control concrete. The aggregate absorption capacity was analized with the presaturation methods achieved and in function of its state of humidity, to evaluate the total and effective water/cement ratios. The effect of these two parameters, both in consistency and compressive strength of recycled concrete, was studied. Finally, the concrete made with 50% and 100% of the elected recycled mixed aggregate was studied and the following concrete properties were tested: consistency, compressive strength, tensile strength, dynamic modulus of elasticity, length changes, water absorption under vacuum and microscopy. To analize the effect of sulphate content, some controlled quantities of gypsum were artificially added to the recycled concrete. Concretes with two types of cement were made, a cement CEM I 42,5 R with a high content of C3A, that would lead to major expansions and a cement with puzzolanic additions CEM II A-P 42,5 R that would lower the expansive behaviour of concrete. The final results indicate that the use of mixed recycled aggregate in proportions up to 50% make possible to cover the overall demanding strengths within the non structural concrete. Sulphates content can range between 0,8% and 1,9%, in function of the type of cement and the proportion of natural aggregate replacement by mixed recycled one. Both in the case of recycled aggregate and concrete, a comparative study was made between the data coming from the bibliography and those obtained in the experimental study. In several recycled concrete properties, the results were compared to the formulas of Spanish Instruction of Structural Concrete (Instruction EHE-08), to establish some correction coefficients to apply for a non structural recycled concrete.

Nondestructive quantification of chemical and physical properties of fruits by time-resolved reflectance spectroscopy in the wavelength range 650-1000 nm

Time-resolved reflectance spectroscopy can be used to assess nondestructively the bulk (rather than the superficial) optical properties of highly diffusive media. A fully automated system for time-resolved reflectance spectroscopy was used to evaluate the absorption and the transport scattering spectra of fruits in the red and the near-infrared regions. In particular, data were collected in the range 650-1000 nm from three varieties of apples and from peaches, kiwifruits, and tomatoes. The absorption spectra were usually dominated by the water peak near 970 nm, whereas chlorophyll was detected at 675 nm. For ail species the scattering decreased progressively with increasing wavelength. A best fit to water and chlorophyll absorption line shapes and to Mie theory permitted the estimation of water and chlorophyll content and the average size of scattering centers in the bulls; of intact fruits.

Performance of pressure control valves and flow meters precision in operational irrigation-water balance accuracy

In pressure irrigation-water distribution networks, pressure regulating devices for controlling the discharged flow rate by irrigation units are needed due to the variability of flow rate. In addition, applied water volume is used controlled operating the valve during a calculated time interval, and assuming constant flow rate. In general, a pressure regulating valve PRV is the commonly used pressure regulating device in a hydrant, which, also, executes the open and close function. A hydrant feeds several irrigation units, requiring a wide range in flow rate. In addition, some flow meters are also available, one as a component of the hydrant and the rest are placed downstream. Every land owner has one flow meter for each group of field plots downstream the hydrant. Its lecture could be used for refining the water balance but its accuracy must be taken into account. Ideal PRV performance would maintain a constant downstream pressure. However, the true performance depends on both upstream pressure and the discharged flow rate. The objective of this work is to asses the influence of the performance on the applied volume during the whole irrigation events in a year. The results of the study have been obtained introducing the flow rate into a PRV model. Variations on flow rate are simulated by taking into account the consequences of variations on climate conditions and also decisions in irrigation operation, such us duration and frequency application. The model comprises continuity, dynamic and energy equations of the components of the PRV.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Exploring the feasibility of integrating water issues into the CAPRI model

Although numerous modelling efforts have integrated food and water considerations at the farm or river basin level, very few agro-economic models are able to jointly assess water and food policies at the global level. The present report explores the feasibility of integrating water considerations into the CAPRI model. First, a literature review of modelling approaches integrating food and water issues has been conducted. Three agro-economic models, IMPACT, WATERSIM and GLOBIOM, have been analysed in detail. In addition, biophysical and hydrological models estimating agricultural water use have also been studied, in particular the global hydrological model WATERGAP and the LISFLOOD model. Thanks to the programming approach of its supply module, CAPRI shows a high potentiality to integrate environmental indicators as well as to enter new resource constraints (land potentially irrigated, irrigation water) and input-output relationships. At least in theory, the activity-based approach of the regional programming model in CAPRI allows differentiating between rainfed and irrigated activities. The suggested approach to include water into the CAPRI model involves creating an irrigation module and a water use module. The development of the CAPRI water module will enable to provide scientific assessment on agricultural water use within the EU and to analyze agricultural pressures on water resources. The feasibility of the approach has been tested in a pilot case study including two NUTS 2 regions (Andalucia in Spain and Midi-Pyrenees in France). Preliminary results are presented, highlighting the interrelations between water and agricultural developments in Europe. As a next step, it is foreseen to further develop the CAPRI water module to account for competition between agricultural and non-agricultural water use. This will imply building a water use sub-module to compute water use balances.

On-line measurement of soil properties without direct spectral response in near infrared spectral range

So far, the majority of reports on on-line measurement considered soil properties with direct spectral responses in near infrared spectroscopy (NIRS). This work reports on the results of on-line measurement of soil properties with indirect spectral responses, e.g. pH, cation exchange capacity (CEC), exchangeable calcium (Caex) and exchangeable magnesium (Mgex) in one field in Bedfordshire in the UK. The on-line sensor consisted of a subsoiler coupled with an AgroSpec mobile, fibre type, visible and near infrared (vis–NIR) spectrophotometer (tec5 Technology for Spectroscopy, Germany), with a measurement range 305–2200 nm to acquire soil spectra in diffuse reflectance mode. General calibration models for the studied soil properties were developed with a partial least squares regression (PLSR) with one-leave-out cross validation, using spectra measured under non-mobile laboratory conditions of 160 soil samples collected from different fields in four farms in Europe, namely, Czech Republic, Denmark, Netherland and UK. A group of 25 samples independent from the calibration set was used as independent validation set. Higher accuracy was obtained for laboratory scanning as compared to on-line scanning of the 25 independent samples. The prediction accuracy for the laboratory and on-line measurements was classified as excellent/very good for pH (RPD = 2.69 and 2.14 and r2 = 0.86 and 0.78, respectively), and moderately good for CEC (RPD = 1.77 and 1.61 and r2 = 0.68 and 0.62, respectively) and Mgex (RPD = 1.72 and 1.49 and r2 = 0.66 and 0.67, respectively). For Caex, very good accuracy was calculated for laboratory method (RPD = 2.19 and r2 = 0.86), as compared to the poor accuracy reported for the on-line method (RPD = 1.30 and r2 = 0.61). The ability of collecting large number of data points per field area (about 12,800 point per 21 ha) and the simultaneous analysis of several soil properties without direct spectral response in the NIR range at relatively high operational speed and appreciable accuracy, encourage the recommendation of the on-line measurement system for site specific fertilisation.