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We analyze whether eco-innovation has a positive or negative influence on the business performance of companies and, through the complementarity approach, whether the joint implementation of R&D subsidy and R&D cooperation increases or decreases the sum of their respective individual impacts on the business performance. If the joint implementation is substitutive, business performance will be lower than potentially possible, so granting R&D subsidies under the condition of establishing R&D cooperation would not be an adequate policy to promote eco-innovation. The analyses were performed using data from the Technological Innovation Panel (PITEC) of 2013 for Spanish manufacturing companies. Our findings indicate that an eco-innovation-oriented strategy positively affects the labor productivity of companies and that receiving public aid as a consequence of establishing R&D cooperation agreements has a lower effect on labor productivity (non-eco-innovative companies), or the same effect (eco-innovative companies), compared to the sum of the individual impacts of R&D cooperation and R&D subsidy. Consequently, in non-eco-innovative companies the use of subsidized R&D cooperation is inadvisable, while their use in eco-innovative companies is neutral.

We analyzed the relationship between exploration-oriented and exploration-oriented alliances. Through the complementarity approach, three possible relationships were analyzed: complementarity, substitutability, and no relationship. We use Technological Innovation Panel data for Spanish manufacturing firms for 2005–2013. The econometric technique that we used to estimate the coefficients was population-averaged OLS. Our findings suggest that alliance portfolios formed by exploration-oriented and exploration-oriented alliances achieve worse innovation performance than specialized exploration or exploitation portfolios. In addition, we found that a single class of alliance has different impacts on innovation performance depending on whether it is implemented by a young company or a mature company.

In the economic literature, there is a debate on whether technological and non-technological innovations share the same determinants. As a result of this debate, two opposing views have emerged: the distinctive view argues that the determinants of both technologies are different; on the contrary, the integrative view considers that both types of technologies share determinants. The main objective that we pursue in this study is to test which of the two views is prevalent in the service sector of the Spanish economy. Analyses were performed using data from Spanish Technological Innovation Panel for the period 2008–2012. To perform hypothesis tests, the approach of complementarity was used. Our findings indicate that neither of the two approaches has been fully accredited, although the distinctive view is more prevalent. However, this radiography of relations tells us that companies can achieve further increases in productivity if technological innovation and non-technological innovation are impleme...

Purpose Although most of the literature supports the existence of a substitutive relationship between exploration and exploitation, some authors suggest that this relationship is complementary (ambidexterity), and others argue that there is no relationship. This paper aims to introduce organizational innovation into the analysis and discusses which of these three relationships prevails. Design/methodology/approach Analyses were performed using data from Spanish Technological Innovation Panel for the period 2008-2013. It should be emphasized that the use of panel data is essential in the analysis of the interaction of exploration and exploitation, as exploration only makes sense in the long run. Econometric strategy uses a two-stage selection model, estimated using the Wooldridge’s (1995) consistent estimator for panel data with sample selection. To perform the test, the hypothesis uses the approach of complementarity. Findings The results show that the relationships exploration-organizational innovation and exploitation-organizational innovation are complementary, provided that the analysis is performed on companies that simultaneously carry out exploration and exploitation activities, respectively. This indicates that the achievement of ambidexterity is strongly conditioned by the simultaneous realization of organizational innovations. Practical implications Managers and policymakers should be aware that the simultaneous implementation of exploration and exploitation yields better results when the corresponding organizational innovations are also implemented. Originality/value This paper extends the empirical investigation of the relationship between exploration and exploitation, seen in conjunction with organizational innovation, and using the complementarity approach as a research tool.

Private companies want to eliminate outgoing spillovers while policymakers seek to maximize them. With subsidized R&D cooperation agreements both agents partially achieve their objectives. For this reason, in Europe, policymakers grant subsidies for R&D activities with the condition of establishing R&D cooperation agreements. This study explores the relationship of complementarity between R&D subsidy, R&D cooperation and absorptive capacity in the context of its contribution to labor productivity of enterprises. The data used comes from the Technological Innovation Panel (PITEC), managed by the Spanish National Statistics Institute. We selected manufacturing companies in the period 2008–2013. We evaluate the existence of complementarity through the systems approach and the interaction approach. The econometric technique that we used to estimate the coefficients of our empirical model was maximum-likelihood random effects. As a consequence of the low absorptive capacity of Spanish manufacturing firms we find that R&D subsidies and R&D cooperation agreements are not complementary variables, i.e., receiving public subsidies as a result of establishing R&D cooperation agreements has a lower impact on productivity than the sum of the individual impacts of R&D cooperation and R&D subsidies. In consequence, this result calls into question the convenience of using subsidized R&D cooperation agreements as a tool for promoting innovation in EU countries as there are notable differences between the companies in these countries in terms of absorption capacity.

The aim of this paper is to analyze the existence of indications of complementarity/substitutability between the innovation agencies operating in Spain (regional, national, European, and Seventh Framework Programme), which will allow us to determine the corresponding asymmetries in the implementation of the so-called subsidiarity principle. The data used in the study come from the Panel de Innovaci&oacute, n Tecnol&oacute, gica 2015 and 2016 (Spain). The empirical analysis has been carried out by the so-called adoption approach, having previously corrected the selection biases that may be present in the sample. The results obtained indicate that there are indications of substitution between the two Spanish agencies (regional and national), while other relationships between agencies exhibit indications of complementarity. These indications of complementarity/substitutability show that the implementation of the principle of subsidiarity between the two Spanish agencies seem to work correctly, while this implementation is much more diffuse between the two Spanish agencies and the two European agencies. Therefore, these results reveal that there is an obvious asymmetry in the implementation of the principle of subsidiarity between the different agencies. These findings may be an important guide in the decision making of managers. Knowing which agencies are substitutes and which are complementary is extremely relevant information, since it allows the advance determination of which combinations of agencies should be avoided. It also provides policy makers with relevant information for the design of more efficient innovation promotion policies. Finally, this research uses a new methodology for the evaluation of the interaction that takes place between the different public agencies for the promotion of innovation, thus contributing to policy analysts and academics, who conduct such evaluations, have at their disposal a new tool for analysis.

This study analyzes the complementarity of foreign technology acquired under license agreements, technology embedded in machinery and equipment and increase in a company’s productive capacity. We use panel data on Brazilian manufacturing companies from the World Bank Surveys. We used the random effects models, estimated by maximum likelihood. The results indicate that foreign technology, embedded technology and increase of productive capacity have a positive and significant impact on labor productivity. The complementarity test reveals that the relationship between the two technologies analyzed is conditionally substitutive and that the relationship between each of these technologies and increase of productive capacity is conditionally complementary.

In this study, we analyze the main strategies used by multinational companies. In our analysis, we found that companies using a global or transnational strategy usually make vertical foreign direct investments, while those with a multi-domestic strategy make horizontal foreign direct investments. Both structures have strengths and weaknesses for companies and labor unions in terms of confrontation and negotiation. According to the definition of economic globalization, we analyzed the operating margins of both strategies, and we concluded that globalization has greatly favored the interests of multinational corporations.

espanolEste estudio analiza la relacion entre productividad laboral, innovacion radical, innovacion incremental, tecnologia incorporada en maquinaria y equipos, utilizacion de la capacidad productiva y formacion. Los datos utilizados son de empresas espanolas, manufactureras y de servicios, procedentes de la Business Environment and enterprise Performance Survey (BEEPS). La tecnica empleada para estimar los coeficientes del modelo es la regresion minimo cuadratica ordinaria, ya que la variable dependiente (productividad laboral) es continua. Los resultados indican que la innovacion radical y la formacion influyen positiva y significativamente sobre la productividad laboral. La influencia de la tecnologia incorporada tambien es significativa, pero de signo negativo. Finalmente, senalar que las empresas que mas exportan y las de mayor tamano alcanzan mayores niveles de productividad. Los hallazgos encontrados en este estudio tienen implicaciones para los responsables de la politica economica. Los decisores politicos espanoles deben promover y subsidiar la adquisicion de maquinaria y equipos mas eficientes para las empresas que alcanzan menores niveles de productividad, asi como subsidiar la formacion de trabajadores cualificados en el manejo de estos nuevos equipos. Ademas, tambien deben promover y subsidiar el desarrollo de actividades de elevado contenido en I+D para las empresas que consiguen elevados niveles de productividad, a fin de que incrementen su desempeno en innovacion radical. La promocion y subsidiacion de programas de formacion relacionados con la I+D tambien resulta esencial en este tipo de empresas, maxime en un escenario caracterizado por un cambio tecnologico intenso y que se produce con gran rapidez. EnglishThis study analyzes the relationship between labor productivity, radical innovation, incremental innovation, embodied technology in machinery and equipment, utilization of production capacity and training. The data used are from Spanish companies, manufacturing and services, and have been collected by the Business Environment and Enterprise Performance Survey (BEEPS). The technique used to estimate the coefficients of the model is the ordinary least square regression, since the dependent variable (labor productivity) is continuous. The results indicate that radical innovation and training have a significant positive impact on labor productivity. The influence of embodied technology is also significant, but of negative sign. Finally, note that the companies that export and larger achieve higher levels of productivity. The findings of this study have implications for responsible for economic policy. Spanish policy makers should promote and subsidize the purchase of machinery and equipment more efficient for companies that achieve lower levels of productivity, and subsidize the training of workers in the management of these new equipments. They must also promote and subsidize the development of activities high in R&D for companies that achieve high levels of productivity, to increase their performance in radical innovation. The promotion and subsidization of training programs related to R&D is also essential in this type of companies, especially in a scenario characterized by an intense and rapid technological change

This paper analyzes the connection between labour productivity and variables such as radical innovation, incremental innovation, production technology embodied in new machinery and equipment, utilization of productive capacity and training. Furthermore, we test the existence of complementarity between radical innovation, incremental innovation and training. The data used are from Spanish manufacturing and service companies and have been collected by the Business Environment and Enterprise Performance Survey (BEEPS). The results indicate that radical innovation and training have a positive and significant impact on labour productivity. The influence of production technology embodied is also significant but negative. We did not find evidence of complementarity or substitutability between the variables analyzed.

The relationship between different types of innovation is analysed from three different approaches. On the one hand, the distinctive view assumes that the determinants of each type of innovation are different and therefore there is no relationship between them. On the other hand, the integrative view considers that the different types of innovation are complementary. Finally, the product–process matrix framework suggests that the relationship between product innovation and process innovation is substitutive. Using data from Spain belonging to the Technological Innovation Panel (PITEC) for the years 2008, 2009, 2010, 2011 and 2012, we tested which of the three approaches is predominant. To perform the hypothesis test, we used the so-called complementarity approach. We find that there is no unique relation. The nature of the relationship depends on the types of innovation that interact. Our most significant finding is that the relationship between product innovation and process innovation is complementary. This finding contradicts the proposal of the product–process matrix framework. Consequently, the joint implementation of both types of innovation generates a greater impact on the performance of a company than the sum of their separate implementations.

Las relaciones entre los diferentes tipos de innovación han sido analizadas desde dos grandes corrientes enfrentadas. Por un lado, la visión distintiva, que asume que los determinantes de cada tipo de innovación son diferentes y que por tanto cada tipo de innovación contribuye de modo diferente al desempeño de la empresa; por otro, la visión integrativa, que considera que los diferentes tipos de innovación son interdependientes y que su implementación simultánea genera un efecto sinérgico sobre el desempeño de la empresa. Utilizando datos de España procedentes del Panel de Innovación Tecnológica (PITEC) de los años 2008, 2009, 2010 y 2011 analizamos cuál de los dos enfoques resulta predominante. Para la realización de los test de hipótesis utilizamos el denominado enfoque de complementariedad, y para la interpretación de estos test el enfoque exploración-explotación. De las seis restricciones no triviales testadas encontramos que solamente una es complementaria. Por consiguiente, estos resultados confirman el predominio de la visión distintiva, corriente mayoritaria en el ámbito de la literatura sobre innovación.

The relationships between different types of innovation have been analyzed two opposing perspectives. On the one hand, the distinctive view assumes that the determinants of each type of innovation are different and therefore each type of innovation contributes differently to the performance of the company. On the other hand, the integrative view considers that the different types of innovation are interdependent and that their simultaneous implementation generates a synergistic effect on firm performance. Using data Spain belonging to the Technological Innovation Panel (PITEC) for the years 2008, 2009, 2010, and 2011, we determine which of the two approaches is predominant. To perform the hypothesis test, we use the so-called complementarity approach, and for the interpretation of those tests, we use the exploration–exploitation approach. We find out that only one of the six non-trivial restrictions tested is complementary. Therefore, these results confirm the predominance of the distinctive view, which is the predominant stream in the field of innovation literature. Keywords: Innovation, complementarity, exploration, exploitation.

Innovation is a key issue for business competitiveness. The most popular kinds of innovation are product innovation and process innovation. The effect of both types of innovation within a company is seen in the specialist literature from two opposing views: the distinctive view, which considers that both kinds of innovation are independent, and the integrative view, which assumes the existence of complementarities between the two kinds of innovation. The aim of this paper is to explore which of the two approaches dominates the context of both the tourism sector and the Spanish manufacturing sector. With samples taken from the database of the Technological Innovation Panel (PITEC 2008), two binary logistic regressions were conducted in two stages and a correlation test was performed with their residuals. The results show that each of the two types of innovation is independent.

From a sample of Spanish manufacturing businesses, extracted from the 2005 Technological Innovation Panel (PITEC 2005), we suggest a lineal regression model in which we relate the exporting intensity with the product innovation, the process innovation, the sectorial technological intensity, the business extent and the membership to a pool of businesses. In the descriptive and statistical analysis, we obtained that all of these variables have a positive and significant influence on the exporting intensity. Regarding this matter, we have checked that the main influence corresponds to businesses that develop product innovation strategies, are of medium extent, are assigned to sectors of medium‐high technological intensity and belong to a foreign corporate group.

The present study attempts to determine the influence of different sources of technological knowledge on the innovation performance of hospitality companies in Spain (Europe) and analyze the degree of coexistence between innovation strategies in the companies. The paper considers a number of ways of incorporating technology and evaluates the impact of different innovation strategies on innovative performance in hospitality companies, in order to assess the importance of each in the Spanish hospitality industry. Employing data from the 2000 Survey on Technological Innovation, two databases were built with information on the Spanish hospitality industry. The first includes all hospitality companies and the second only companies engaged in innovation activities. With the second database, an analysis of the coexistence of innovation strategies is done by means of seven logit regressions. The results show that the innovation strategies that coexist most frequently are, first, the acquisition of external techno...

In this study, we analyze the main strategies used by multinational companies. In our analysis, we found that companies using a global or transnational strategy usually make vertical foreign direct investments, while those with a multi-domestic strategy make horizontal foreign direct investments. Both structures have strengths and weaknesses for companies and labor unions in terms of confrontation and negotiation. According to the definition of economic globalization, we analyzed the operating margins of both strategies, and we concluded that globalization has greatly favored the interests of multinational corporations. En este estudio, se exponen y describen las principales estrategias de las empresas multinacionales. Sobre este particular, constatamos que las empresas que siguen una estrategia global o transnacional suelen llevar a cabo inversiones directas en el extranjero de naturaleza vertical, mientras que las que siguen una estrategia multidoméstica realizan inversiones directas en el extranjero de naturaleza horizontal. Ambas estructuras ofrecen fortalezas y debilidades a las empresas, ya las fuerzas organizadas del trabajo (sindicatos) en sus procesos de confrontación y negociación. Según lo que se ha venido denominando globalización de la economía, analizamos los márgenes de maniobrabilidad de ambos contendientesy concluimos que la globalización ha favorecido en gran medida los intereses de las empresas multinacionales. Este estudo analisa as principais estratégias que implementam as empresas multinacionais. Na análise, constatamos que as empresas que seguem uma estratégia global ou multinacional realizam investimentos directos do tipo vertical no estrangeiro, enquanto as que seguem uma estratégia multidoméstica realizam investimentos directos e horizontais no estrangeiro. Ambas estruturas têm pontos fortes e fracos para as empresas e para as forças organizadas em sindicatos, em seus processos de confrontação e negociação. À luz do que se denomina globalização da economia, analisamos as margens de trabalho das partes, e concluímos que a globalização tem favorecido, em grande parte, os interesses das empresas multinacionais.

In this study, we pursue two objectives. First, we analyse the influence of product, process, and non-technological innovation on environmental performance. Second, we explore the existence of complementarities or substitutabilities between the different combinations of these three types of innovations to learn which combinations improve or worsen environmental performance. The analyses were performed using data from the 2013 Technological Innovation Panel (PITEC) for Spanish manufacturing companies. We use the two-stage least-squares method as an instrumental variable estimator, which allows us to control the endogeneity and obtain consistent estimators. Our findings indicate that product innovation and process innovation have a negative influence on environmental performance. Likewise, we have also found that the simultaneous implementation of product innovation and process innovation is unconditionally substitutive and that the joint implementation of process innovation and non-technological innovation is conditionally substitutive. This result reinforces the position of those researchers who have pointed out that the association between a greater technology orientation and a better firm environmental performance is probably too simplistic. Finally, it should be emphasized that only non-technological innovation contributes to achieving better environmental performance and that the joint implementation of product innovation and non-technology innovation is conditionally complementary.

En este trabajo se describen brevemente los principales hitos tecnológicos que han ido marcando y configurando el sector gráfico, y se aborda su delimitación. Asimismo, se lleva a cabo un análisis comparativo con el sector manufacturero español, estudiando el comportamiento de ambos sectores en los ámbitos de atomización y dispersión empresarial, inversiones realizadas, subvenciones recibidas, capacidad de generación de empleo y demografía. Finalmente, también se aborda la singularidad que el sector gráfico español representa en el ámbito del comercio exterior, y algunos de los retos que las actuales fuerzas globalizadoras de la economía le plantean.

RESUMEN Introduccion. En este trabajo se contrasta como la cooperacion empresarial a nivel de I+D, el tamano y la pertenencia al sector grafico condicionan la participacion de las empresas manufactureras innovadoras en los sistemas de ayuda publica a la innovacion. Material y metodos. A partir de los microdatos de la “Encuesta sobre innovacion tecnologica 1998-2000”, del Instituto Nacional de Estadistica (INE), se construye una base de datos con las empresas manufactureras espanolas que realizan actividades de innovacion. Posteriormente, mediante metodos estadisticos univariantes y multivariantes, contrastamos si cooperacion, tamano y pertenencia al sector grafico condicionan la participacion de las empresas manufactureras innovadoras en los sistemas de ayuda publica a la innovacion, asi como la direccion de dicho condicionamiento. Resultados. Los contrastes realizados nos indican que una mayor cooperacion entre empresas a nivel de I+D y un mayor tamano influyen positivamente en el grado de participacion de las empresas en los sistemas de ayuda publica a la innovacion. Por el contrario, la pertenencia al sector grafico, en relacion al resto del sector manufacturero, influye negativamente en el grado de participacion de las empresas en los sistemas de ayuda publica a la innovacion. Discusion. Las Administraciones publicas buscan fomentar el desarrollo de la innovacion entre las empresas manufactureras facilitando financiacion a las empresas que cooperan en el ambito de la I+D. Asimismo, las ayudas publicas a la innovacion tienen como objetivo preferente las empresas de mayor tamano, mientras que las empresas pertenecientes al sector grafico tienen menores probabilidades de conseguir financiacion publica para sus proyectos innovadores que las restantes empresas del sector manufacturero espanol.

Filtration experiments in batch concentration mode (with recycling of the retentate stream) of the cork processing wastewater were performed in laboratory filtration membrane equipment, by using four commercial membranes: two UF membranes with MWCO of 20,000 and 5000 Da, and two NF membranes with an approximate MWCO of 150-300 Da. The filtration experiments of the selected wastewater were performed by modifying the most important operating variables: transmembrane pressure, tangential velocity, temperature, and the nature and MWCO of the membranes. The evolution of the cumulative permeate volumes and permeate fluxes with processing time were analysed, and it was established that the steady-state permeate flux was reached for a volume retention factor of 2. The effect of the mentioned operating conditions on this steady-state permeate flux was discussed. The effectiveness of the filtration treatments was determined by the evaluation of the rejection coefficients for several parameters, which measure the global pollutant content of the effluent: COD, absorbance at 254 nm, tannic content, color, and ellagic acid. Finally, the resistances in series model was used for the evaluation of the resistances to the permeate flux, and it was concluded that the contribution to the total resistance of the fouling resistance (combined external plus internal) was higher than the inherent resistance of the clean membrane.

Diazinon is a widely used organophosphorus insecticide that is an important pollutant in aquatic environments. The chemical removal of diazinon has been studied using UV radiation, ozone, Fenton's reagent, UV radiation plus hydrogen peroxide, ozone plus hydrogen peroxide and photo-Fenton as oxidation processes. In the photodegradation process the observed quantum yields had values ranging between 2.42 × 10−2 and 6.36 × 10−2 mol E−1. Similarly, the ozonation reaction gave values for the rate constant ranging between 0.100 and 0.193 min−1. In the combined systems UV/H2O2 and O3/H2O2 the partial contributions to the global oxidation reaction of the direct and radical pathways were deduced. In the Fenton's reagent and photo-Fenton systems, the mechanism of reaction has been partially discussed, and the predominant role of the radical pathway pointed out. Additionally, the rate constant for the reaction between diazinon and the hydroxyl radicals was determined, with the value 8.4 × 109 L mol−1 s−1 obtained. A comparison of the different oxidation systems tested under the same operating conditions revealed that UV radiation alone had a moderate oxidation efficiency, which is enhanced in the case of ozone, while the most efficient oxidant is the photo-Fenton system. Copyright © 2007 Society of Chemical Industry

The chemical oxidation of two herbicide derivatives of the phenylurea group—diuron and isoproturon—has been carried out by means of chlorine, in the absence and in the presence of bromide ion. Apparent second-order rate constants for the reactions between chlorine and the herbicides were determined to be below 0.45 L mol−1 s−1. Hypobromous acid reacts faster with the investigated herbicides, especially with isoproturon (kapp = 24.8 L mol−1 s−1 at pH 7). While pH exerts a negative effect on the bromination rate, the maximum chlorination rate was found to be at circumneutral pH. In a second stage, the oxidation of each compound was conducted in different natural waters, in order to simulate the processes which take place in water purification plants. Again, chlorine was used as an oxidant, and bromide ion was added in some experiments with the aim of producing the more reactive HOBr oxidant. The herbicide oxidation rate was inversely proportional to the organic matter content of the natural water. However, the formation of trihalomethanes (THMs) was directly proportional to the organic matter content and constitutes a limitation for the application of chlorine during drinking water treatment. Finally, the evolution of herbicide concentration was modeled and predicted by applying a kinetics approach based on the rate constants for the reactions between the herbicides and the active oxidants. Copyright © 2007 Society of Chemical Industry

Experiments on alachlor degradation by ozonation alone and combined with hydrogen peroxide using different surface waters have been conducted in a reactor bubble column and a kinetic model of the advanced oxidation process has been proposed. Variables studied were the nature of the surface water (four surface waters were treated), pH (3.5–9.7) and hydrogen peroxide to ozone mass ratio at the column inlet (0.1–1.85 g g−1). Data on residence time distribution, rate constants and the absorption kinetic regime were considered to prepare the kinetic model, which was also based on the axial dispersion model of non-ideal flow. The model gives good predictions of alachlor and hydrogen peroxide conversions and the fraction of dissolved ozone (deviations were lower than ±15%) although it fails, in some cases, to yield accurate estimates of the observed experimental trends of concentrations in water at the reactor column outlet. The calculated results were close to those obtained from the more classical N well-mixed tanks-in-series model (deviations with this model were lower than ±20%). It is concluded that quantitative deviations from experimental observations were likely due to the lack of rate data on ozone reactions with organic matter present in the surface waters investigated. © 2002 Society of Chemical Industry

El objetivo de este artículo es analizar los determinantes de la cooperación en investigación y desarrollo (I+D) de las empresas innovadoras del sector manufacturero español, prestando especial atención a las ayudas públicas a la innovación, una variable poco frecuente en esta clase de estudios académicos. Los datos utilizados en el estudio proceden del Panel de Innovación Tecnológica del año 2010 (PITEC, 2010). El análisis empírico se llevó a cabo mediante la realización de una regresión logística binaria de naturaleza bietápica, con la finalidad de eliminar el potencial sesgo de selección que pudiera estar presente. Los resultados indican que las empresas que exhiben una mayor probabilidad de cooperar son aquellas que reciben alguna clase de ayuda pública a la innovación, realizan mayores gastos internos en investigación y desarrollo (I+D), pertenecen a un grupo de empresas, tienen un mayor tamaño y utilizan métodos de protección legal para evitar que otras empresas se apropien de los resultados de sus investigaciones. La principal conclusión del estudio es que la concesión de ayudas públicas a la innovación, bajo la condicionalidad de establecer acuerdos de cooperación debe practicar una cierta clase de discriminación entre sectores de alta y baja intensidad tecnológica.

The ozonation of atrazine in different waters (ultrapure and surface waters) has been studied in continuous bubble contactors with kinetic modelling purposes. Three ozonation processes have been considered: ozonation alone and combined with hydrogen peroxide or UV radiation. The kinetic models are based on a molecular and free radical mechanism of reactions, reaction rate and mass transfer data and non-ideal flow analysis models for gas and water phases through the contactors (the tanks in series model and the dispersion model). The models predict well the experimental concentrations of atrazine, dissolved ozone and hydrogen peroxide both at non-steady state and steady state regimes. From both experimental and calculated results, atrazine conversions are observed to be highly dependent on the nature of water where ozonation is carried out. As far as removal of atrazine and oxidation intermediates are concerned, ozone combined with UV radiation resulted in the most effective ozonation process among the three studied.

Aqueous oxidation of three polynuclear aromatic hydrocarbons, fluorene, phenanthrene and acenaphthene with the combination of hydrogen peroxide and ferrous ion, Fenton reagent, has been studied. The effect of variables such as concentration of both reactants, pH and presence of bicarbonate ion and humic substances has been investigated. Products resulting from oxidation have also been identified. From experimental results and kinetic data determined the process is confirmed as an advanced oxidation involving the generation of hydroxyl radicals. Oxidation rates are even higher than those from other advanced oxidation systems involving ozone, UV radiation and hydrogen peroxide. Reactivity is in the following decreasing order: Phenanthrene > Fluorene > Acenaphthene.

The oxidation of two wastewaters collected from distillery and tomato processing plants with UV radiation (254 nm) alone and combined with hydrogen peroxide has been investigated. Distillery wastewaters are refractory to UV radiation but the presence of hydrogen peroxide leads to different COD reductions which indicates that the process is mainly due to the action of radicals. Tomato wastewaters, on the other hand, show a higher reactivity even with UV radiation alone. The quantum yield for tomato wastewaters with an initial COD of 930 mg O2l−1 was found to be 0.7 mol O2 photon−1 and decreased with reaction time. The combined effect of UV radiation and hydrogen peroxide at a 0.01 M concentration on tomato wastewaters leads to about 25% COD reduction while TOC was unchanged. The contribution of radical reactions in this process was higher than 60%.

The UV photolysis and H2O2/UV advanced oxidation of two intermediate compounds of the degradation of atrazine in water, deethylatrazine and deisopropylatrazine, have been studied. The influence of hydrogen peroxide and bicarbonate ion concentrations was observed both in organic-free water and in surface waters. Both UV photolysis and UV/H2O2 oxidation techniques lead to significant rates of elimination of these compounds, although they were lower in surface waters, likely due to the presence of natural radical scavengers. However, in the presence of 0.01 M bicarbonate ion, degradation rates were similar regardless of the type of water used. A kinetic study of both techniques was also conducted. Quantum yields and rate constants of the reaction between the hydroxyl radical and both intermediates were determined.

The UV/H 2 O 2 oxidation of trichloroethylene, TCE, and 1,1,1 trichloroethane, TCA, in water was studied. Oxidation rates depend on the initial hydrogen peroxide concentration with maximum values in the presence of concentrations of 10 −2 M which represents rates of about 5 and 250 times higher than those obtained from volatilization alone for TCA and TCE, respectively. In the case of TCE, contribution of direct photolysis is negligible. In natural waters, oxidation rates of TCA and TCE slightly decreases compared to those in laboratory prepared waters. When concentrations of hydrogen peroxide applied are higher than 10 −2 M, TCA is mainly removed by volatilization since hydrogen peroxide consumes most of radicals generated. On the contrary, free radical oxidation continues to be the principal step of removal in the case of TCE since the rate constant of its reaction with hydroxyl radicals is approx. 65 times higher than that of the reaction OH-TCA. Experiments with high concentration of hydrogen peroxide (>10 −2 M) allow to determine the rate constants of TCE-OH and TCA-OH reactions that were found to be 1.8×10 9 and 2.0×10 7 M −1 s −1 , respectively.

[ES] A partir de los microdatos de la "encuesta sobre innovación tecnológica 1998-2000" se construye una base de datos con las empresas manufactureras españolas que realizan actividades de innovación. Posteriormente, mediante las pruebas Chi-cuadrado de Pearson y Mann-Whitney, contrastamos si el tamaño condiciona la participación de las empresas manufactureras innovadoras en los sistemas de ayuda pública a la innovación; asimismo, a través de los índices de Kendall y Spearman evaluamos la dirección de dicho condicionamiento. Al respecto, los contrastes realizados nos indican que la variable tamaño se encuentra relacionada con la variable financiación pública, y que son las empresas de mayor tamaño las que más se benefician de las ayudas públicas a la innovación. [EN] From the microinformation of the “survey on technological innovation 1998-2000” a database is constructed by the manufacturing Spanish companies that realize activities of innovation. Subsequently, by testing Pearson Chi-square and Mann-Whitney, test whether the size of companies influences the participation of innovative manufacturing companies in the systems of public support for innovation as well as the address of that conditioning. In this regard, the contrasts made indicate that the variable size is related to the variable public funding, and which are the larger companies which benefit most from public support for innovation.

Ozonation of two phenols, resorcinol and phloroglucinol known as strong trihalomethane precursors, have been studied using surface renewal and eddy diffusivity absorption theories. Rate constants of ozonations have been calculated at different pH and temperature and compared to those predicted from the film theory. Reaction factors were also calculated from these theories and compared each other showing a very good agreement. The major difference was observed when in some cases, film theory predicts an instantaneous reaction while surface renewal and eddy diffusivity theories consider that the reaction is fast of second order.

Kinetic equations derived from surface renewal and eddy diffusivity theories for fast and instantaneous kinetic regimes of absorption have been applied to the results of the ozonation of 1,3-cyclohexanedione (CYC) in water. This has allowed the determination of the rate constant of the direct reaction of ozone with CYC and the liquid phase volumetric mass transfer coefficient of the system. The results obtained are close to those reported in the preceding paper (SOTELO et al., 1991) when using the film theory. However, the ozone partial pressure necessary to reach the instantaneous kinetic regime is higher for the case of the theories applied in this work.

The reaction between ozone and 1,3-cyclohexanedione in aqueous solutions at different pH was investigated from the point of view of the film theory. The rate of ozone absorption is accompanied by a second order irreversible reaction with 1,3-cyclohexanedione. The kinetic regime of absorption was found to change from fast (the reaction being of pseudo first order) to instantaneous, according to the ozone partial pressure applied. The former kinetic regime allows the determination of the reaction rate constant, while the latter leads to the volumetric mass transfer coefficient of the system.

The reaction rate between ozone and o–cresol in aqueous solution at pH 2 has been studied. According to the absorption theories, the kinetic regime of the process in the experimental conditions investigated, corresponds to an irreversible fast pseudo-first order reaction between non-dissociated o-cresol and ozone. Similar values for the rate constant are deduced from the different theories. Therefore the film theory, having a simple mathematical basis, seems to be the most appropriate model for this kinetic study.

Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 degrees C and pH 7 were determined to be 110.9, 0.004 and 191.6 M(-1) s(-1) for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L(-1) was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

This paper proposes a model that relates public funding, company size, technological intensity, permanent R&D, business group membership and corporate strategy to the likelihood that firms will cooperate in R&D. To test the validity of the model, we built a database of Spanish manufacturing firms with innovation activities based on the ‘Survey on Technological Innovation of Enterprises 2000’, conducted by the National Statistics Institute (INE) of Spain. The test showed that all variables have a positive effect on the likelihood of R&D cooperation, but medium-sized enterprises and enterprise groups that belong to the EU and outside of the EU showed no significant influence on the probability of cooperation.

Based on the data of the ‘survey on technological innovation 1998–2000’, a database with the Spanish manufacturing companies that make innovation activities was constructed. Later, we formulated a model, in which the corporative strategy, the differentiation strategy, the costs leadership strategy, the organisational structure and the absorption capacity of ID in addition, its corresponding relation with the probability of cooperation is not significant.

A kinetic model for the removal of trichloroethylene and trichloroethane from natural waters with ozonation processes has been proposed and tested at different conditions implying the presence of hydrogen peroxide or UV radiation. The model is constituted by the mol balance equations of the organochlorine compound, ozone (both in water and gas phases) and hydrogen peroxide and predicts the concentration of these substances with reaction time at different conditions. Main variables that affect the oxidation rate are gas flow rate (volumetric mass transfer and volatility coefficients), concentration of hydrogen peroxide and intensity of UV radiation. The kinetic model predicts reasonably well experimental concentrations of TCA during the ozonation at low gas flow rate (thus minimizing the importance of volatility) but overestimates the experimental concentrations when UV radiation or hydrogen peroxide are simultaneously applied to the ozonation of TCE, specially at 20 Lh‐1 gas flow rate. The presen...

Ozone decomposition in water in the presence of different salts has been studied. The stability of ozone varies depending on the salt nature and the pH. At low pH, molecular phosphoric acid has a positive influence upon ozone conversion. At neutral and basic pH, ozone decomposes through a radical mechanism, whose termination step depends on the type of ionic species present. So, at pH 6 in the absence of salts or in the presence of chloride ions it is proposed a second order termination step. In addition, the direct reaction between ozone and chloride ion has to be considered. When there are sulphate, phosphate or carbonate ions present in the water, the termination step changes to first order due to the hydroxyl radical scavenging effect of these ions. Hence, these ions estabilize molecular ozone in water.

The advanced oxidation of some polynuclear aromatic hydrocarbos, PAHs (fluorene, phenanthrene and acenaphthene) in surface waters where they were added was studied with ozone alone or combined with hydrogen peroxide or UV radiation (254 nm) or with the combination of the latter two. The influence of water nature (surface and organic‐free waters) and type of oxidation was investigated. Oxidation rates in surface waters are generally slower than those in organic‐free waters. PAHs are in any case removed from surface waters at high oxidation rates with half life ranging from less than 1 minute when ozone is used in combination to UV radiation to 1 to 3 minutes for the other advanced oxidations. Application of UV radiation alone lead to the lowest degradation rates with half lifes of more than 6 minutes. Among the PAHs studied, fluorene is the one with the lowest oxidation rates regardless of type of advanced oxidation applied.

The kinetics of continous direct ozonation of trichloroethylene, a water priority pollutant, is investigated. The influence of water flow type on the kinetics is studied by the use of the residence time distribution function. In accordance with this, the actual reactor used behaves as two perfectly mixed continous stirred reactors. A kinetic model accounting for rates of volatilization, direct ozonation and mass transfer together with non‐idealk water flow is presented. The results obtained indicate that water flow type should be considered to, predict more accurately removal rates of trichloroethylene during direct ozonation.

Ozonation of trichloroethylene, TCE and 1,1,1 trichloroethane, TCA in water has been studied. The effect of gas flow rate, pH, ozone partial pressure and water nature has been investigated. These variables exert positive effects on the elimination rates. Gas flow rate effect is specially important in the case of TCA which, at 20 Lh‐1, is mainly transferred from the water to the air rather than being decomposed through ozonation. On the contrary, TCE is mainly oxidised through hydroxyl radicals. The rate constant of the TCE‐ozone direct reaction was found to be 17.1 M‐1s‐1 which confirms that direct ozonation represents a rather poor contribution (in most cases between 2 to 5%) of the total TCE elimination rate. Therefore, ozonation of these compounds is basically an advanced oxidation process due to the participation of hydroxyl radicals. At high gas flow rates (20 Lh‐1) ozonation rates of VOC elimination were similar in ultrapure laboratory and surface waters used, except for the case of TCE that at 2.5 ...