Application of cyclodextrins in agrochemistry

9 pages, 69 references.Peer Reviewe

Mechanisms of interaction between montmorillonite and 3-aminotriazole

The adsorption of aminotriazole, at its solution pH, with montmorillonite saturated with different cations has been studied. A pesticide-montmorillonite complex is formed through interlamellar cations which are not displaced. Aminotriazole is situated mostly as a polarized molecule around Mg2+ and Zn2+ cations, removing a great amount of water. In Na+- and Li+-montmorillonite, the pesticide remains as a non-polarized molecule, hydration water being retained in the interlamellar space; the pesticide is coordinated to interlamellar cations through water bridges. For all samples a proportion of cationic aminotriazole is also adsorbed, the amount being greater with increasing polarizing power of the interlamellar cation; consequently, in Fe3+-montmorillonite all the aminotriazole adsorbed is in the cationic form.The authors acknowledge the Direcci6n General de Investigaci6n Científica y Técnica, Spain, for financial support of this work through Project PB87-0240.Peer Reviewe

Síntesis y eficacia de formulaciones de liberación lenta del herbicida Mesotriona

Ponencia presentada en el XV Congreso de la Sociedad Española de Malherbología SEMh 2015 “La Malherbología y la Transferencia Tecnológica” Sevilla, 19 al 22 de octubre de 2015[ES]: Se ha comprobado la eficacia de formulaciones desarrolladas mediante complejos surfactante-sepiolita en la reducción de la lixiviación del herbicida mesotriona. Entre las formulaciones desarrolladas se ha escogido aquella que presentaba un perfil de liberación más lento en ensayos in vitro. Al aplicarse en columnas de suelo se observó una lixiviación del herbicida y acumulación con la formulación comercial en los segmentos inferiores a diferencia de la formulación desarrollada, que se correlacionaba con un incremento de la bioeficacia en los segmentos superiores. En experimentos en parcelas de campo, a diferencia de la formulación comercial, no se observó un rebrote de las malas hierbas al usar la formulación desarrollada. [EN]: Synthesis and efficiency of slow release formulations of the herbicide mesotrione. The bioefficay of developed formulations based on surfactant-sepiolite complexes for reduced leaching of the herbicide mesotrione was tested. The formulation with a slower release pattern in in-vitro experiments was chosen for soil column and field experiments. In soil columns, the commercial formulation was leached and accumulated in the lower segments unlike the synthesized formulation, with a higher amount retained in the upper segments which was also correlated with a higher bioefficacy. In field experiments, a regrowth of weeds with the clay-based formulation was not observed, unlike the commercial formulation.Esta investigación ha recibido financiación a través de los proyectos CMT2009-07425 (MEC) cofinanciado por el Fondo Europeo de Desarrollo Regional (FEDER) y el Proyecto Bilateral Hispano-Argentino PRI-PIBAR-2011-1393 (MINECO-MINCYT). Carmen Galán agradece la beca Predoctoral disfrutada y asociada al Proyecto de Excelencia P09- RNM-4581.Peer Reviewe

Evolución y análisis filogenético de las comunidades microbianas desarrolladas como respuesta al aumento de los niveles de fenantreno en un suelo contaminado por PAHs

Trabajo presentado al citado Congreso que tuvo lugar del 21-24, de septiembre, 2009, en Almería, España.Las comunidades microbianas de los suelos contaminados con hidrocarburos aromáticos poli cíclicos (PAHs) presentan gran biodiversidad. Esta biodiversidad puede relacionarse con la respuesta a niveles elevados de PAHs. En este trabajo se presenta el estudio y la caracterización de las comunidades microbianas de un suelo contaminado principalmente con hidrocarburos aromáticos poli cíclicos (5LO), mediante técnicas basadas en ADN y técnicas de cultivo. Se ha estudiado la evolución de las comunidades como respuesta al aumento de la concentración de fenantreno.Peer reviewe

Assisted attenuation of a soil contaminated by diuron using hydroxypropyl-β-cyclodextrin and organic amendments

7 páginas.-- 1 Grafico.-- 3 figuras.-- 2 tablas.-- 59 referenciasDiuron desorption and mineralisation were studied on an amended and artificially contaminated soil. The amendments used comprised two different composted organic residues i.e., sewage sludge (SS) mixed with pruning wastes, and urban solid residues (USR), and two different solutions (with inorganic salts as the micronutrients and hydroxypropyl-β-cyclodextrin (HPBCD)). After applying micronutrients to activate the soil flora, 15.5% mineralisation could be reached after 150 days, indicating that the soil has a potential capacity to mineralise the herbicide through biostimulation-assisted attenuation. Diuron mineralisation was also improved when HPBCD solutions were applied. Indeed, the extent of herbicide mineralisation reached 29.7% with this application. Moreover, both the lag phase and the half-life time (DT50) were reduced to 33 and 1778 days, respectively, relative to the application of just micronutrients (i.e., 39 and 6297 days, respectively). Organic amendments were also applied (i.e., USR and SS) on the contaminated soil: it was found that the diuron mineralisation rate was improved as the amendment concentration increased. The joint application of all treatments investigated at the best conditions tested was conducted to obtain the best diuron mineralisation results. The micronutrient amendment plus 4% USR or SS amendment plus HPBCD solution (10-fold diuron initially spiked) caused an extent of diuron mineralisation 33.2 or 46.5%, respectively.This work was supported by the Spanish Ministry of Science and Innovation (co-funded by the Fondo Europeo de Desarrollo Regional, FEDER) under the research project CTM2009-07335 and Junta de Andalucía (RNM 894).Peer reviewe

Comparative effects of several cyclodextrins on the extraction of PAHs from an aged contaminated soil

7 páginas.-- 3 figuras.-- 2 tablas.-- 52 referencias.-- Supplementary dataThe objective of the present study was to characterise the polycyclic aromatic hydrocarbons (PAHs) content of an aged contaminated soil and to propose remediation techniques using cyclodextrins (CDs). Four CDs solutions were tested as soil decontamination tool and proved more efficient in extracting PAHs than when an aqueous solution was used; especially two chemically modified CDs resulted in higher extraction percentages than natural β-CD. The highest extraction percentages were obtained for 3-ring PAHs, because of the appropriate size and shape of these compounds relative to those of the hydrophobic cavities of the CDs studied. A detailed mechanistic interpretation of the chemical modification of CDs on the extraction of the different PAHs has been performed, and connected with the role that the different hydrophobicities of the PAHs play in the extraction behaviour observed for the 16 PAHs, limiting their accessibility and the remaining risk of those PAHs not extractable by CDs. © 2013 Elsevier Ltd. All rights reserved.The authors thank to Dr. J.R. Gallego from the Universidad de Oviedo for providing the contaminated soil sample. Support from projects CTM2006-04626 and CTM2009-07335, Spanish Ministry of Science and Innovation (co-funded by Fondo Europeo de Desarrollo Regional, FEDER), are greatly appreciated. M.A. Sánchez-Trujillo acknowledges a research contract from CSIC (JAEPre 0800763) cofinanced by Fondo Social Europeo (FSE).Peer Reviewe

Effects of soil characteristics on metribuzin dissipation using clay-gel-based formulations

Metribuzin (MTB) is a herbicide widely used for weed control in growing soybeans and other crops and has been identified in many parts of the world as a groundwater contaminant. To prepare controlled-release formulations (CRFs) of MTB, it was entrapped within a sepiolite-gel-based matrix with one of two proportions of clay/herbicide and used as either a gel or powder after freeze-drying. To determine how its persistence in soil is affected by formulation and soil type, MTB was applied as a CRF or commercial formulation (CM) to soils with different properties. MTB dissipation in all soils investigated was reduced when the herbicide was applied as CRFs, especially in the case of sandy soil and the freeze-dried formulations, with DT50 values of 57.5 and 104.1 days, respectively, versus 24.8 days for CM. A positive relationship between degradation rates, bioactivity, and soil pH was found. MTB adsorption-desorption studies on these soils were also performed, and no relationship between adsorption-desorption and the degradation rate of MTB was found, possibly because of the low adsorption capacity of the studied soils. MTB when applied as a CRF remains active longer than CM, avoiding the need to use more frequently herbicide applications.This work was supported by the Spanish Ministry of Education and Science (MEC) through Research Projects AGL 2005-00164, by Junta de Andaluc ́ıa (project P06-FQM-01909), and by AECID (project A/016047/08).Peer Reviewe

Novel system for reducing leaching of the herbicide metribuzin using clay-gel-based formulations

Metribuzin is an herbicide widely used for weed control that has been identified as a groundwater pollutant. It contaminates the environment even when it is used according to the manufacturer's instructions. To reduce herbicide leaching and increase weed control, new controlled release formulations were developed by entrapping metribuzin within a sepiolite-gel-based matrix using two clay/herbicide proportions (0.5/0.2 and 1/0.2) (loaded at 28.6 and 16.7% a.i.) as a gel (G28, G16) or as a powder after freeze-drying (LF28, LF16). The release of metribuzin from the control released formulations into water was retarded, when compared with commercial formulation (CF) except in the case of G28. The mobility of metribuzin from control released formulations into soil columns of sandy soil was greatly diminished in comparison with CF. Most of the metribuzin applied as control released formulations (G16, LF28 and LF16) was found at a depth of 0-8 cm depth. In contrast, residues from CF and G28 along the column were almost negligible. Bioassays from these control released formulations showed high efficacy at 0-12 cm depth. The use of these novel formulations could minimize the risk of groundwater contamination while maintaining weed control for a longer period.Peer Reviewe

Decontamination of polycyclic aromatic hydrocarbons and nonylphenol from sewage sludge using hydroxypropyl-β-cyclodextrin and evaluation of the toxicity of leachates

11 páginas.-- 2 tablas.-- 3 figuras.-- 61 referenciasA decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg-1. Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union's draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg-1 for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-β-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90 % of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1 %. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture. © 2013 Springer-Verlag Berlin Heidelberg.Support from projects CTM2006-04626 and CTM2009-07335, Spanish Ministry of Science and Innovation (cofunded by Fondo Europeo de Desarrollo Regional, FEDER), are greatly appreciated. M.A. Sánchez-Trujillo acknowledges a research contract from Consejo Superior de Investigaciones Científicas (CSIC, JAEPre 0800763) cofinanced by Fondo Social Europeo (FSE).Peer Reviewe

Uso potencial de arcillas modificadas con metales para la obtención de formulaciones de liberación lenta de herbicidas.

9 páginas., 5 gráficos, 2 tablas y 9 referencias. Versión extendida de la comunicación presentada en la "XIX Reunión Científica de la Sociedad Española de Arcillas - SEA05", celebrada en Salamanca del 26 al 28 de Septiembre de 2005. Enlace a la web de la Sociedad Española de Arcillas http://www.sea-arcillas.es/publicacionesSEA.htm[EN]Abstract A slow release system of the herbicide imazapyr was designed by adsorption on pillared clays. Pillared clays based on aluminum and mixed aluminum-copper solutions were synthesized. The aim was to check whether the introduction into the pillars of a metal complexing the herbicide molecules enhanced the sorption and release properties of the clay for the herbicide. A commercial aluminum pillared clay was also examined as a potential sorbent. The chemical analysis data as well as those of X-ray diffraction show that copper from pillaring solutions was partially introduced, and the basal spacing were increased about 9 Å in good agreement with the size of the Keggin ion. The textural properties indicate a reduction in the micro- and mesoporosity of the pillared clays after pillaring with copper solutions. The largest the copper content in the mixed Al-Cu pillared clays the largest the decrease in the surface area. However, imazapyr adsorption increased up to three-fold compared to the commercial pillared clay, and desorption percentages from the Cu-Al pillared clays were three-fold lower than the commercial one, whose desorption was completely reversible. These preliminary results show the potential use of Cu-Al pillared clays for the development of slow release formulations of the herbicide imzapyr, unlike those whose pillars are only made of aluminum.[ES]Resumen En el presente trabajo se ha intentado desarrollar un sistema de liberación lenta del herbicida imazayr mediante su adsorción en arcillas pilareadas. Se han sintetizado arcillas pilareadas con aluminio y con soluciones mixtas Cu-Al, a fin de comprobar si la formación de pilares mixtos de aluminio con un metal complejante del herbicida mejoraba las propiedades de adsorción y liberación del mismo. También se ha estudiado el empleo potencial de una arcilla pilareada comercial formada con pilares exclusivos de aluminio. Los resultados de análisis químico así como de difracción de rayos X muestran que parte del cobre de las soluciones pilareantes se ha introducido en las arcillas finales, cuyos espaciados basales presentan un incremento de aproximadamente 9 Å, que se corresponde con el tamaño del ión Keggin. Las propiedades texturales indican una disminución tanto de la microporosidad como de la mesoporosidad en las arcillas tras su pilarización con soluciones de Cu-Al, que es tanto mayor cuanto mayor es el contenido de Cu. A pesar de la reducción en la superficie de estas arcillas sintetizadas con Cu, la adsorción de imazapyr incrementaba hasta 3 veces con respecto a la arcilla pilareada comercial. A su vez los porcentajes de desorción en la arcillas pilareadas con Cu-Al eran hasta tres veces inferiores a los correspondientes a la arcilla pilareada comercial, cuya desorción era prácticamente reversible. Estos resultados preliminares avalan el uso potencial de arcillas pilareadas con Cu-Al para el desarrollo de formulaciones de liberación lenta del herbicida imazapyr, a diferencia de aquellas en las que los pilares se encuentran formados únicamente por aluminio.Peer Reviewe