Textural properties of synthetic clay-ferrihydrite associations

13 páginas, 8 figuras, 3 tablas, 35 referencias.Kaolinite-ferrihydrite and montmorillonite-ferrihydrite associations were prepared following a procedure based on the Russell method for the synthesis of ferrihydrite and the texture of the clay-ferrihydrite complexes was studied using different techniques. The textural properties of kaolinite were little affected by the Fe association, showing only a slight .increase in the specific surface area measured by nitrogen adsorption and a decrease in the largest pores (>10 micro m), as measured by mercury porosimetry. In contrast, the nitrogen specific surface area of the montmorillonite complexes was much higher than that of the clay without Fe and the pore structure depended on the amounts of Fe in the complexes. Application of the fractal approach to nitrogen adsorption data indicated that the surface roughness (microporosity) was greater for the complexes prepared from diluted Fe(III) solutions, in agreement with the information obtained from classical interpretation of the adsorption isotherms (shape of the isotherms and t-plots).This study has been supported partially by the CICYT through the project AMB-93-81 , AMB-96-445-C02- 02, the EU project EV 5V-CT94-0470, and by the Research Group RNM 124 of Junta de Andalucía. R. Celis also thanks the Spanish Ministry of Education and Science for his PFPU fellowship.Peer reviewe

Ensayo de arcillas modificadas con materia orgánica soluble para la eliminación de Cu y Zn

La contaminación por metales pesados es un tema de gran preocupación. Entre las diversas actividades que contribuyen a aumentar la presencia de metales pesados en el medio ambiente, se encuentra la agricultura. Por ejemplo, el uso de fertilizantes de tipo fosforados y algunos fungicidas incrementan la aparición Cu y Zn en aguas de zonas agrícolas e incluso residuales de la industria agroalimentaria. La eliminación de metales pesados mediante el uso de minerales de la arcilla tipo montmorillonita ha sido objeto de numerosos trabajos (Barbier et al., 2000) dada su alta capacidad de adsorción principalmente asociada a su capacidad de intercambio catiónico (CIC), fácil accesibilidad de su interlámina y a la presencia de grupos hidroxilos de los bordes de ruptura de la capa octaédrica.Este trabajo ha sido financiado con los proyectos de la Junta de Andalucía (P11-AGR-7400) y RECUPERA 2020 (MCINN_CSIC). E. Durán agradece la concesión de la Beca Predoctoral FPI asociada (P11-AGR-7400). A Fertiormont y a Spuny Morón por el material suministrado.Peer Reviewe

Decoloración y detoxificación de aguas de alperujo mediante el empleo de esmectitas e hidrotalcita

2 páginas.-- 1 figura.-- 1 tablas.-- 8 referencias.-- Poster presentado en XXIV Reunión de la Sociedad Española de Arcillas Sevilla. Libro de Resúmenes: Noviembre de 2015 en Sevilla.El alperujo es el residuo sólido del proceso de extracción de aceite de oliva virgen en dos fases, que se produce en grandes cantidades en diversas regiones españolas y cuyo empleo como fertilizante y enmendante de suelos, una vez compostado, facilita una salida sostenible para estos contribuyendo favorablemente al secuestro de carbono (1,2) No obstante también puede dar lugar a algunos efectos adversos: a) Coloración de las aguas, b) Deterioro del suelo por su acidez y sales, c) Solubilización, transporte y lixiviación de algunos metales pesados y plaguicidas (3, 4) y d) Fitotoxicidad sobre plantas y microrganismos acuáticos, si no han sido previamente compostados o tratados (5). Sobre la hipótesis del conocido potencial de los materiales arcillosos de interaccionar con la materia orgánica soluble (MOS) de suelos, sedimentos o residuos (4, 6), el objetivo del presente trabajo ha sido evaluarla capacidad de arcillas catiónicas y aniónicas como adsorbentes de la MOS procedente de alperujo, responsable de los efectos adversos descritos. La finalidad última es el posible desarrollo y utilidad de adsorbentes naturales para reducir la coloración y toxicidad de aguas de lavado de almazaras, o para su posible co-aplicación con alperujo a suelos agrícolas disminuyendo los efectos adversos sobre semillas o plantas o para corregir los efectos de un vertido puntual incontrolado.Este trabajo ha sido financiado a través de los proyectos P07-AGR-03077 y P11-AGR-07400 y AGR-264 de la Junta de Andalucía, cofinanciados por FEDER y FSE; y el Convenio RECUPERA 2020 del MINECO-CSIC.Peer reviewe

Tricyclazole-clay complexes as potential smart delivery systems: release in water and environmental fate in alluvial and sandy soils

Natural mineral clays (SWy-2, CTI and SH) were modified with natural inorganic cation (Fe3+) and the biopolymer (chitosan (ch)) to increase the adsorption capacity for tricyclazole. Three ways to prepare tricyclazole-clay complexes (ground mixing, GM, weak complex, WC and strong complex, SC) were assayed with the aim to develop possible components for controlled release formulations (CRFs) of this fungicide. The greatest adsorption (> 93%) was measured in the natural clays modified with Fe3+. The release of tricyclazole in water was higher for GMs of SWch6 (77%), SWch4 (84%) and CTIFe (85%). No significant differences were observed in the dissipation in soil of tricyclazole applied as commercial product or as formulation. However, the leaching of the fungicide depended on the type of soil: tricyclazole was not detected in any leachate from the soil with higher clay content (alluvial) whereas the SWch6 weak complex (WC) reduced the leaching of tricyclazole (65%) as compared to the commercial formulation (75%) in a sandy soil after 60 days. This last tricyclazol-clay complex could be considered as appropriate component for CRF, to be used in sandy soils. The other modified clays assayed, showing very high, strong and irreversible adsorption could find application as filters to eliminate tricyclazole from contaminated waters. Clay-fungicide interaction mechanisms are discussed and related to their soil and water behavior.CSIC (JAE-Doc program), MINECO (AGL2011-23779 project) and Junta de Andalucía (P11-AGR-7400), co-funded by EU FEDER-FSE (OP 2009-2013) funding.Peer Reviewe

Comportamiento del herbicida fluometurón en un suelo de olivar enmendado con organoarcilla bajo condiciones de campo

7 páginas, 6 figuras, 3 tablas, 19 referencias.-- Publicado en el capítulo Tema 2 – Propriedades e processos do solo.-- Congreso celebrado en septiembre de 2012, en Islas Azores, Portugal.Las arcillas modificadas con cationes orgánicos u organoarcillas suelen presentar buenas propiedades adsorbentes para muchos plaguicidas y se han propuesto en diferentes aplicaciones dirigidas a reducir la movilidad de estos compuestos tras su aplicación a los suelos agrícolas. En trabajos previos realizados en condiciones de laboratorio, observamos que la modificación de una montmorillonita de Wyoming (SWy- 2) con el catión orgánico de origen natural espermina (SPERM) daba lugar a una organoarcilla (SW- SPERM) con una afinidad muy elevada por el herbicida fluometurón y que la adición de SW-SPERM a suelos aumentaba el poder de retención de éstos y reducía la lixiviación del herbicida. El objetivo del presente trabajo ha sido evaluar el efecto de la adición de SW-SPERM a un suelo de olivar mediterráneo en la persistencia, lixiviación y escorrentía del herbicida fluometurón bajo condiciones reales de campo. Se utilizaron dos parcelas de 4 x 1 m, una sin enmendar y otra enmendada con SW-SPERM a 0.2 kg/m2, a las que se aplicó fluometurón a 3 kg/ha. Se tomaron muestras de suelo a diferentes tiempos y profundidades (0-5, 5-10, 10-20 and 20-30 cm) y se determinó la cantidad de herbicida en las mismas así como en las aguas de escorrentía procedentes de cada parcela. En la parcela enmendada con SW-SPERM, el herbicida persistió durante más tiempo en los primeros 0-5 cm de suelo, presentando una menor lixiviación en comparación con la parcela sin enmendar. Las concentraciones de herbicida en las aguas de escorrentía de la parcela enmendada con SW-SPERM fueron superiores que en las aguas procedentes de la parcela sin enmendar, probablemente por la mayor persistencia del herbicida en el horizonte más superficial y el posible arrastre de herbicida asociado a partículas de arcilla. Los resultados apuntan a que SW-SPERM podría ser útil como enmienda de suelos para aumentar el tiempo de residencia de fluometurón en la zona radicular, controlando el posible riesgo por escorrentía del herbicida o aplicando la organoarcilla a una cierta profundidad en el suelo para protegerla de la escorrentía.Este trabajo ha sido financiado por la Junta de Andalucía a través del proyecto P07-AGR-03077, cofinanciado con fondos FEDER-FSE a través del programa Operativo de Andalucía 2007-2013. Beatriz Gámiz agradece a la Junta de Andalucía la concesión de una beca de Formación de Personal Investigador, cofinanciada con fondos FSE.Peer Reviewe

Adsorción-desorción de los metales pesados Pb(II) y Hg(II) por modelos de partículas coloidales del suelo

4 páginas, 2 figuras, 1 tabla, 3 referencias.-- Publicado en el Capítulo IV: Contaminación y Medio Ambiente.-- Trabajo presentado a la XVII Reunión Científica de la Sociedad Española de Arcillas, celebrada en Elche (Alicante) y Castellón, del 27-29 de noviembre de 2002.El destino de los metales pesados en el medio ambiente está controlado por las reacciones de adsorción a los coloides del suelo. Por otro lado, las interacciones entre los constituyentes del suelo pueden alterar significativamente la cantidad y naturaleza de la superficie expuesta por los coloides del suelo para la adsorción de contaminantes. Por tanto, las predicciones sobre la extensión de la adsorción basadas en la suma de las capacidades adsorbentes de los constituyentes individuales del suelo pueden desviarse de lo que ocurre en la naturaleza (1). En la bibliografia han sido poco estudiadas las interacciones entre contaminantes y adsorbentes polifásicos, aunque en la última década ha aumentado la atención dada al estudio del comportamiento de modelos de asociaciones coloidales para obtener una interpretación más realista del proceso de adsorción en el suelo (2). En este trabajo se han determinado las capacidades adsorbentes de modelos de partículas coloidales binarias y ternarias que contienen montmorillonita (SW), ferrihidrita (Fh) y ácido húmico (AH) para dos contaminantes inorgánicos, los metales pesados Pb(lI) y Hg(II), Y se compararon con las capacidades de adsorción de los constituyentes individuales. Las partículas modelos se prepararon en el laboratorio y se caracterizaron por análisis elemental, espectroscopía infrarroja, difracción de rayos X y medidas de superficie específica. Se estudió la adsorción-desorción de Pb(lI) y Hg(ll) por parte de los diferentes adsorbentes y se utilizaron las técnicas de espectroscopía infrarroja y difracción de rayos X para analizar los mecanismos de interacción.Este trabajo ha sido financiado por el proyecto del MCYT REN2001-1700-C02- 01/TECNO y por el grupo RNM124 del PAI de la Junta de AndalucíaPeer reviewe

Influence of biochar on the enantioselective behavior of the chiral fungicide metalaxyl in soil

Comunicación oral presentada en la EGU General Assembly 2015, held 12-17 April, 2015 in Vienna, Austria. Id.15367Chiral pesticides comprise an emerging and important class of organic pollutants currently, accounting for more than a quarter of used pesticides. Consequently, the contamination problems caused by chiral pesticides are concern matter and factors affecting enantioselective processes of chiral pesticides in soil need to be understood. For example, certain soil management practices, such as the use of organic amendments, can affect the enantioselective behavior of chiral pesticides in soils. Recently, biochar (BC), i.e. organic matter subjected to pyrolysis, has been proposed as organic amendment due to beneficial properties such as its high stability against decay in soil environments and its apparent ability to influence the availability of nutrients. BC is considered to be more biologically inert as compared to otherforms of organic carbon. However, its side-effects on the enantioselectivity of processes affecting the fate of chiral pesticides is unknown. The aim of this study was to assess the effect of biochar (BC) on the enantioselectivity of sorption, degradation, and leaching of the chiral fungicide metalaxyl in an agricultural soil. Amending the soil with BC (2% w/w) resulted in 3 times higher sorption of metalaxyl enantiomers compared to unamended soil, but no enantioselectivity in the process was observed. Moreover, both enantiomers showed some resistance to be desorbed in BC-amended soil compared to unamended soil. Dissipation studies revealed that the degradation of metalaxylwas more enantioselective in the unamended soil than in BC-amended soil. In unamended soil, R-metalaxyl(biologically active) and S- metalaxyl had half-lives (t1/2) of 3 and 34 days, respectively. BC enhanced the persistence of both enantiomers in the soil, with R-metalaxyl being degraded faster (t1/2=43 days) than S-metalaxyl (t1/2= 100 days). The leaching of both S-and R-metalaxyl was almost suppressed after amending the soil with BC; less than 10% of the fungicide applied to soil columns was recovered in leachates, in contrast to significantly higher percentages leachedin unamended soil, being the process more enantioselective in the latter case. Finally, total recoveries of both enantiomers were greater for BC-amended soil columns than for unamended soil columns, indicating reduced degradation in BC- amended soil. Our findings illustrated the ability of biochar to modify the enantioselectivity behavior of metalaxyl in soil by its high sorption capacity. BC could contribute to reduce the current agronomic doses used for chiral pesticides to deplete the contamination problems associated with their use, and also to act as an immobilizing amendment in soil remediation strategies.MINECO (AGL2011-23779), FACCE-JPI (Designchar4food), JA (AGR-264) and FEDERF-SE (OP 2007-2013).Peer Reviewe

Comparison of inorganic and biohybrid layered silicates as adsorbents and carriers of herbicide imazamox for smart control of Striga and Orobanche spp.weeds

Poster presentado en el International Conference on Structural Nano Composites 20-21 May 2014 in Madrid, Spain, pag. 53 (2014) (NANOSTRUC 2014)Parasitic plants as Striga and Orobanche spp. are controlled by the systemic herbicide imazamox, which has to act at early stages of weed seeds germination in the root zone. Imazamox is an ionic herbicide with high water solubility and soil mobility: high risk of water contamination and loss of efficacy.CSIC (JAE-­‐Doc), MINECO (AGL2011-­‐23779), JA (AGR-­‐264 and P11-­‐AGR-­7400) with FEDER-­‐FSE (OP2009-­‐13); BASF for technical imazamox and M.A. Adelino for SW-­CHs samples.Peer Reviewe

Enantioselective behavior of metalaxyl in soil under repeated applications

10 páginas.-- 5 imágenes.-- 2 tablas.-- 52 referenciasBACKGROUND: Soil incubation and column leaching experiments were conducted to address the question of whether the type of formulation (unsupported versus clay supported) and repeated applications of the chiral fungicide (RS)-metalaxyl affected the enantioselectivity of its dissipation and leaching in a slightly alkaline, loamy sand agricultural soil. RESULTS: Regardless of the type of formulation and the number of fungicide applications, the R-enantiomer of metalaxyl was degraded faster than the S-enantiomer, but the individual degradation rates of R- and S-metalaxyl were highly affected by the different application regimes assayed (t1/2 = 2-104 days). Repeated applications accelerated the degradation of the biologically active R-metalaxyl enantiomer, whereas they led to slower degradation of the non-active S-metalaxyl enantiomer. The type of formulation had less influence on the dissipation rates of the enantiomers. For all formulations tested, soil column leachates became increasingly enriched in S-enantiomer as the number of fungicide applications was increased, and application of metalaxyl to soil columns as clay-based formulations reduced the leaching of both enantiomers. CONCLUSION: Pesticide application conditions can greatly influence the enantioselective dissipation of chiral pesticides in soil, and hence are expected to exert a great impact on both the biological efficacy and the environmental chiral signatures of pesticides applied as mixtures of enantiomers or racemates to agricultural soils. © 2015 Society of Chemical Industry.This work has been financed by the Spanish Ministry of Economy and Competitiveness (MINECO Project AGL2011-23779) and Junta de Andalucía (Research Group AGR-264), cofinanced by European FEDER-FSE funds (Operative Programme 2007-2013). Beatriz Gámiz thanks the Junta de Andalucía for a post-doctoral contract linked to the project P07-AGR-03077. María Adelino thanks MINECO for a predoctoral FPI fellowship. The authors also thank MJ Calderón (IRNAS, CSIC),MI Cardo (IRNAS, CSIC) and P Franco (Chiral Technologies Europe) for technical assistance, and Dr. S Redondo and Dr. E Mateos (University of Seville) for their help with the statistical treatment of the data.Peer reviewe

Assessing the Effect of Organoclays and Biochar on the Fate of Abscisic Acid in Soil

10 páginas.-- 6 figuras.-- 2 tablas.-- 56 referencias.-- The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jafc.6b03668The potential use of allelopathic and signaling compounds as environmentally friendly agrochemicals is a subject of increasing interest, but the fate of these compounds once they reach the soil environment is poorly understood. This work studied how the sorption, persistence, and leaching of the two enantiomers of the phytohormone abscisic acid (ABA) in agricultural soil was affected by the amendments of two organoclays (SA-HDTMA and Cloi10) and a biochar derived from apple wood (BC). In conventional 24-h batch sorption experiments, higher affinity toward ABA enantiomers was displayed by SA-HDTMA followed by Cloi10 and then BC. Desorption could be ascertained only in BC, where ABA enantiomers presented difficulties to be desorbed. Dissipation of ABA in the soil was enantioselective with S-ABA being degraded more quickly than R-ABA, and followed the order unamended > Cloi10-amended > BC-amended > SA-HDTMA-amended soil for both enantiomers. Sorption determined during the incubation experiment indicated some loss of sorption capacity with time in organoclay-amended soil and increasing sorption in BC-amended soil, suggesting surface sorption mechanisms for organoclays and slow (potentially pore filling) kinetics in BC-amended soil. The leaching of ABA enantiomers was delayed after amendment of soil to an extent that depended on the amendment sorption capacity, and it was almost completely suppressed by addition of BC due to its irreversible sorption. Organoclays and BC affected differently the final behavior and enantioselectivity of ABA in soil as a consequence of dissimilar sorption capacities and alterations in sorption with time, which will affect the plant and microbial availability of endogenous and exogenous ABA in the rhizosphere.This work has been financed by the Spanish Ministry of Economy and Competitiveness (MINECO Project AGL2014- 51897-R), EU FACCE-JPI (Designchar4food Project), and Junta de Andalucıa (P011-AGR-7400 and Research Group ́ AGR-264), cofinanced with European FEDER funds. The use of trade, firm, or corporation names in this paper is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by the U.S. Department of Agriculture, the Agricultural Research Service, or the Instituto de Recursos Naturales y Agrobiologıa de Sevilla ́ (IRNAS-CSIC) of any product or service to the exclusion of others that may be suitablePeer reviewe