Marco-Brown, J.L.; Undabeytia, T.; Torres Sánchez, R.M.; dos Santos Afonso, M."Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite" (2017) Environmental Science and Pollution Research. 24(11):10410-10420
Estamos trabajando para incorporar este artículo al repositorio
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor


Slow-release formulations of the herbicide picloram (PCM, 4-amino-3,5,6-trichloropyridine-2-carboxylic acid) were designed based on its adsorption on pillared clays (pillared clays (PILCs)) for reducing the water-polluting risk derived from its use in conventional formulations. Fe–Al PILCs were synthesized by the reaction of Na+-montmorillonite (SWy-2) with base-hydrolyzed solutions of Fe and Al. The Fe/(Fe + Al) ratios used were 0.15 and 0.50. The PCM adsorption isotherms on Fe–Al PILCs were well fitted to Langmuir and Freundlich models. The PCM adsorption capacity depended on the Fe content in the PILCs. Slow-release formulations were prepared by enhanced adsorption of the herbicide from PCM-cyclodextrin (CD) complexes in solution. CDs were able to enhance up to 2.5-fold the solubility of PCM by the formation of inclusion complexes where the ring moiety of the herbicide was partially trapped within the CD cavity. Competitive adsorption of anions such as sulfate, phosphate, and chloride as well as the FTIR analysis of PCM-PILC complexes provided evidence of formation of inner sphere complexes of PCM-CD on Fe–Al PILCs. Release of the herbicide in a sandy soil was lower from Fe–Al PILC formulations relative to a PCM commercial formulation. © 2017, Springer-Verlag Berlin Heidelberg.


Documento: Artículo
Título:Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite
Autor:Marco-Brown, J.L.; Undabeytia, T.; Torres Sánchez, R.M.; dos Santos Afonso, M.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, Buenos Aires, C1428EHA, Argentina
Instituto de Química Física de los Materiales, Medio Ambiente y Energía de la Facultad de Ciencias Exactas y Naturales (INQUIMAE), CONICET-Universidad de Buenos Aires, Buenos Aires, Argentina
Instituto de Investigación e Ingeniería Ambiental (3iA), CONICET, Escuela de Ciencia y Tecnología, UNSAM, 25 de Mayo y Francia (1650), San Martín, Argentina
Institute of Natural Resources and Agrobiology (IRNAS-CSIC), Reina Mercedes 10. Apdo. 1052, Sevilla, 41080, Spain
Centro de Tecnología en Recursos Minerales y Cerámica (CETMIC), CONICET-CCT La Plata-CIC, Camino Centenario y 506 CC (49), M. B. Gonnet, B1897ZCA, Argentina
Palabras clave:Adsorption; Fe–Al pillared montmorillonite; Picloram; Slow-release formulations; adsorption; anion; herbicide; hydrolysis; montmorillonite; pesticide residue; sandy soil; water pollution; aluminum silicate; bentonite; clay; herbicide; picloram; adsorption; Adsorption; Aluminum Silicates; Bentonite; Herbicides; Picloram
Página de inicio:10410
Página de fin:10420
Título revista:Environmental Science and Pollution Research
Título revista abreviado:Environ. Sci. Pollut. Res.
CAS:aluminum silicate, 12183-80-1, 1302-93-8, 1318-74-7, 1335-30-4, 61027-90-5; bentonite, 1302-78-9; picloram, 1918-02-1; Aluminum Silicates; Bentonite; clay; Herbicides; Picloram


  • Akelah, A., Novel utilizations of conventional agrochemicals by controlled release formulations (1996) Mater Sci Eng C, 4, pp. 83-98
  • Ali, I., Asim, M., Khan, T.A., Low cost adsorbents for the removal of organic pollutants from wastewater (2012) J Environ Manag, 113, pp. 170-183. , COI: 1:CAS:528:DC%2BC38Xhs12lsbbL
  • Alromeed, A.A., Scrano, L., Bufo, S.A., Undabeytia, T., Slow-release formulations of the herbicide MCPA by using clay-protein composites (2015) Pest Manag Sci, 71, pp. 1303-1310. , COI: 1:CAS:528:DC%2BC2cXhvFGlsLfP
  • Biggar, J.W., Mingelgrin, U., Cheung, M.W., Equilibrium and kinetics of adsorption of picloram and parathion with soils (1978) J. Agr. Food Chem., 26, pp. 1306-1312. , COI: 1:CAS:528:DyaE1cXlslCqurw%3D
  • Campos, E.V.R., de Oliveira, J.L., Fraceto, L.F., Singh, B., Polysaccharides as safer release systems for agrochemicals (2014) Agron Sustain Dev, 35, pp. 47-66
  • Carrizosa, M.J., Calderón, M.J., Hermosín, M.C., Cornejo, J., Organosmectites as sorbent and carrier of the herbicide bentazone (2000) Sci Total Environ, 247, pp. 285-293. , COI: 1:CAS:528:DC%2BD3cXhvVKgsrk%3D
  • Celis, R., Hermosin, M.C., Cornejo, L., Carrizosa, M.J., Cornejo, J., Clay-herbicide complexes to retard picloram leaching in soil (2002) Int J Environ An Ch, 82, pp. 503-517. , COI: 1:CAS:528:DC%2BD3sXmt12itA%3D%3D
  • Cheung, M.W., Biggar, J.W., Solubility and molecular-structure of 4-amino-3,5,6-trichloropicolinic acid in relation to pH and temperature (1974) J. Agr. Food Chem., 22, pp. 202-206. , COI: 1:CAS:528:DyaE2cXksV2isbk%3D
  • Delcour, I., Spanoghe, P., Uyttendaele, M., Literature review: impact of climate change on pesticide use (2015) Food Res Int, 68, pp. 7-15
  • Eggleston, C.M., Hug, S., Stumm, W., Sulzberger, B., dos Santos, A.M., Surface complexation of sulfate by hematite surfaces: FTIR and STM observations (1998) Geochim. Cosmochim. Ac., 62, pp. 585-593. , COI: 1:CAS:528:DyaK1cXivVeit7c%3D
  • Entry, J.A., Sojka, R.E., Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils (2008) J Environ Manag, 87, pp. 364-372. , COI: 1:CAS:528:DC%2BD1cXmtFKgsb8%3D
  • Essington, M.E., (2004) Soil and water chemistry, an integrative approach, , CRC Press, Boca Raton
  • Specifications and evaluations for agricultural pesticides (2007) Picloram, ,
  • Galán-Jiménez, M.C., Mishael, Y.G., Nir, S., Morillo, E., Undabeytia, T., Factors affecting the design of slow release formulations of herbicides based on clay-surfactant systems (2013) A Methodological Approach PLoS ONE, 8
  • Gupta, V.K., Suhas (2009) Application of low-cost adsorbents for dye removal—a review. J Environ Manag, 90, pp. 2313-2342
  • Hall, K.E., Ray, C., Ki, S.J., Spokas, K.A., Koskinen, W.C., Pesticide sorption and leaching potential on three Hawaiian soils (2015) J Environ Manag, 159, pp. 227-234. , COI: 1:CAS:528:DC%2BC2MXps1Cnsr4%3D
  • Haynes, D., Müller, J., Carter, S., Pesticide and herbicide residues in sediments and seagrasses from the Great Barrier Reef World Heritage Area and Queensland Coast (2000) Mar Pollut Bull, 41, pp. 279-287. , COI: 1:CAS:528:DC%2BD3MXhs1ahug%3D%3D
  • He, L.M., Zelazny, L.W., Baligar, V.C., Ritchey, K.D., Martens, D.C., Ionic strength effects on sulfate and phosphate adsorption on γ-alumina and kaolinite: triple-layer model (1997) Soil Sci Soc Am J, 61, pp. 784-793. , COI: 1:CAS:528:DyaK2sXjvVOqsrc%3D
  • Higuchi, T., Connors, K., Phase solubility techniques (1965) Advances in analytical chemistry instrumentation, pp. 117-212. , Reilly CN, (ed), Interscience, New York, NY
  • Jozefaciuk, G., Muranyi, A., Fenyvesi, E., Effect of cyclodextrins on surface and pore properties of soil clay minerals (2001) Environ. Sci. Technol., 35, pp. 4947-4952. , COI: 1:CAS:528:DC%2BD3MXotlKrs7w%3D
  • Kashyap, P.L., Xiang, X., Heiden, P., Chitosan nanoparticle based delivery systems for sustainable agriculture (2015) Int J Biol Macromol, 77, pp. 36-51. , COI: 1:CAS:528:DC%2BC2MXktFKrtb0%3D
  • Kenawy, E.R., Sherrington, D.C., Akelah, A., Controlled release of agrochemical molecules chemically bound to polymers (1992) Eur Polym J, 28, pp. 841-862. , COI: 1:CAS:528:DyaK38Xlt1Khu7s%3D
  • Kooner, Z.S., Jardine, P.M., Feldman, S., Competitive surface complexation reactions of sulfate and natural organic carbon on soil (1995) J Environ Qual, 24, pp. 656-662. , COI: 1:CAS:528:DyaK2MXntFOqur4%3D
  • Lagaly, G., Pesticide-clay interactions and formulations (2001) Appl Clay Sci, 18, pp. 205-209. , COI: 1:CAS:528:DC%2BD3MXjtFegsLs%3D
  • Loewy, M., Kirs, V., Carvajal, G., Venturino, A., Pechen De D’Angelo, A.M., Groundwater contamination by azinphos methyl in the Northern Patagonic Region (Argentina) (1999) Sci Total Environ, 225, pp. 211-218. , COI: 1:CAS:528:DyaK1MXhtVWnsbw%3D
  • Loring, J.S., Karlsson, M., Fawcett, W.R., Casey, W.H., Attenuated total reflection-Fourier-transform infrared and 27 Al-nuclear magnetic resonance investigation of speciation and complexation in aqueous AI(III)-picolinate solutions (2000) Geochim Cosmochim Ac, 64, pp. 4115-4129. , COI: 1:CAS:528:DC%2BD3cXosFaku78%3D
  • Maqueda, C., Villaverde, J., Sopeña, F., Undabeytia, T., Morillo, E., Novel system for reducing leaching of the herbicide metribuzin using clay-gel-based formulations (2008) J. Agr. Food Chem., 56, pp. 11941-11946. , COI: 1:CAS:528:DC%2BD1cXhtl2ltbvP
  • Maqueda, C., Villaverde, J., Sopeña, F., Undabeytia, T., Morillo, E., Effects of soil characteristics on metribuzin dissipation using clay-gel-based formulations (2009) J. Agr. Food Chem., 57, pp. 3273-3278. , COI: 1:CAS:528:DC%2BD1MXivFSnsL8%3D
  • Marco-Brown, J.L., Barbosa-Lema, C.M., Torres Sánchez, R.M., Mercader, R.C., dos Santos, A.M., Adsorption of picloram herbicide on iron oxide pillared montmorillonite (2012) Appl Clay Sci, 58, pp. 25-33. , COI: 1:CAS:528:DC%2BC38XksVKnu7Y%3D
  • Marco-Brown, J.L., Areco, M.M., Torres Sánchez, R.M., dos Santos, A.M., Adsorption of picloram herbicide on montmorillonite: kinetic and equilibrium studies (2014) Colloid Surface A, 449, pp. 121-128. , COI: 1:CAS:528:DC%2BC2cXltFantrk%3D
  • Marco-Brown, J.L., Trinelli, M.A., Gaigneaux, E.M., Torres Sánchez, R.M., Dos Santos, A.M., New insights on the structure of the picloram-montmorillonite surface complexes (2015) J Colloid Interf Sci, 444, pp. 115-122. , COI: 1:CAS:528:DC%2BC2MXitVyntQ%3D%3D
  • Mishra, T., Mohapatra, P., Parida, K.M., Synthesis, characterisation and catalytic evaluation of iron-manganese mixed oxide pillared clay for VOC decomposition reaction (2008) Appl Catal, B, 79, pp. 279-285. , COI: 1:CAS:528:DC%2BD1cXovVyhtg%3D%3D
  • Morillo, E., Sánchez-Trujillo, M.A., Villaverde, J., Madrid, F., Undabeytia, T., Effect of contact time and the use of hydroxypropyl-β-cyclodextrin in the removal of fluorene and fluoranthene from contaminated soils (2014) Sci Total Environ, 496, pp. 144-154. , COI: 1:CAS:528:DC%2BC2cXht1KhsbbL
  • Nir, S., Undabeytia, T., Yaron-Marcovich, D., El-Nahhal, Y., Polubesova, T., Serban, C., Rytwo, G., Rubin, B., Optimization of adsorption of hydrophobic herbicides on montmorillonite preadsorbed by monovalent organic cations: interaction between phenyl rings (2000) Environ Sci Technol, 34, pp. 1269-1274. , COI: 1:CAS:528:DC%2BD3cXhsVakt70%3D
  • Osteryoung, J., Whittaker, J.W., Picloram—solubility and acid-base equilibria determined by normal pulse polarography (1980) J. Agr. Food Chem., 28, pp. 95-97. , COI: 1:CAS:528:DyaL3cXntFSitQ%3D%3D
  • Palma, G., Sanchez, A., Olave, Y., Encina, F., Palma, R., Barra, R., Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile (2004) Chemosphere, 57, pp. 763-770. , COI: 1:CAS:528:DC%2BD2cXos1yksLo%3D
  • Pérez-Martínez, J.I., Ginés, J.M., Morillo, E., Moyano, J.R., 1H-nuclear magnetic resonance and phase solubility studies of the stoichiometries in 2,4-D: α-and β-cyclodextrins inclusion complexes (2000) J Inclusion Phenom, 37, pp. 171-178
  • Qi, Y., Donahoe, R.J., The environmental fate of arsenic in surface soil contaminated by historical herbicide application (2008) Sci Total Environ, 405, pp. 246-254. , COI: 1:CAS:528:DC%2BD1cXhtFOjurbO
  • Sánchez-Jiménez, N., Sevilla, M.T., Cuevas, J., Rodríguez, M., Procopio, J.R., Interaction of organic contaminants with natural clay type geosorbents: potential use as geologic barrier in urban landfill (2012) J Environ Manag, 95
  • Sarbak, Z., Structural and surface properties of anion-activated clay (1994) Mater Chem Phys, 39, pp. 91-97. , COI: 1:CAS:528:DyaK2MXisFegs7w%3D
  • Schipper, P.N.M., Vissers, M.J.M., van der Linden, A.M.A., Pesticides in groundwater and drinking water wells: overview of the situation in the Netherlands (2008) Water Science and Technology, pp. 1277-1286
  • Szejtli, J., Introduction and general overview of cyclodextrin chemistry (1998) Chem Rev, 98, pp. 1743-1753. , COI: 1:CAS:528:DyaK1cXksV2itrw%3D
  • Undabeytia, T., Sopeña, F., Sánchez-Verdejo, T., Villaverde, J., Nir, S., Morillo, E., Maqueda, C., Performance of slow-release formulations of alachlor (2010) Soil Sci Soc Am J, 74, pp. 898-905. , COI: 1:CAS:528:DC%2BC3cXmtVWms7c%3D
  • Undabeytia, T., Recio, E., Maqueda, C., Morillo, E., Gómez-Pantoja, E., Sánchez-Verdejo, T., Reduced metribuzin pollution with phosphatidylcholine-clay formulations (2011) Pest Manag Sci, 67, pp. 271-278. , COI: 1:CAS:528:DC%2BC3MXhs1yltbk%3D
  • Undabeytia, T., Recio, E., Maqueda, C., Sánchez-Verdejo, T., Balek, V., Slow diuron release formulations based on clay-phosphatidylcholine complexes (2012) Appl Clay Sci, 55, pp. 53-61. , COI: 1:CAS:528:DC%2BC38XktVyktw%3D%3D
  • Undabeytia, T., Galán-Jiménez, M.C., Gómez-Pantoja, E., Vázquez, J., Casal, B., Bergaya, F., Morillo, E., Fe-pillared clay mineral-based formulations of imazaquin for reduced leaching in soil (2013) Appl Clay Sci, 80-81, pp. 382-389. , COI: 1:CAS:528:DC%2BC3sXht1SrtLrJ
  • Wang, Y., Gao, Z., Shen, F., Li, Y., Zhang, S., Ren, X., Hu, S., Physicochemical characteristics and slow release performances of chlorpyrifos encapsulated by poly(butyl acrylate- co -styrene) with the cross-linker ethylene glycol dimethacrylate (2015) J Agr Food Chem, 63, pp. 5196-5204. , COI: 1:CAS:528:DC%2BC2MXnvV2kur0%3D
  • Wenz, G., Han, B.H., Müller, A., Cyclodextrin rotaxanes and polyrotaxanes (2006) Chem Rev, 106, pp. 782-817. , COI: 1:CAS:528:DC%2BD28XhsVOmt7s%3D
  • Yan, H., Chen, X., Feng, Y., Xiang, F., Li, J., Shi, Z., Wang, X., Lin, Q., Modification of montmorillonite by ball-milling method for immobilization and delivery of acetamiprid based on alginate/exfoliated montmorillonite nanocomposite (2015) Polym Bull, 73, pp. 1185-1206
  • Yáñez, C., Cañete-Rosales, P., Castillo, J.P., Catalán, N., Undabeytia, T., Morillo, E., Cyclodextrin inclusion complex to improve physicochemical properties of herbicide bentazon: exploring better formulations (2012) PLoS One, 7


---------- APA ----------
Marco-Brown, J.L., Undabeytia, T., Torres Sánchez, R.M. & dos Santos Afonso, M. (2017) . Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite. Environmental Science and Pollution Research, 24(11), 10410-10420.
---------- CHICAGO ----------
Marco-Brown, J.L., Undabeytia, T., Torres Sánchez, R.M., dos Santos Afonso, M. "Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite" . Environmental Science and Pollution Research 24, no. 11 (2017) : 10410-10420.
---------- MLA ----------
Marco-Brown, J.L., Undabeytia, T., Torres Sánchez, R.M., dos Santos Afonso, M. "Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite" . Environmental Science and Pollution Research, vol. 24, no. 11, 2017, pp. 10410-10420.
---------- VANCOUVER ----------
Marco-Brown, J.L., Undabeytia, T., Torres Sánchez, R.M., dos Santos Afonso, M. Slow-release formulations of the herbicide picloram by using Fe–Al pillared montmorillonite. Environ. Sci. Pollut. Res. 2017;24(11):10410-10420.