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«: AGROCHEMICALS: FATE IN FOOD AND THE ENVIRONMENT PROCEEDINGS OF A SYMPOSIUM, ROME, 7 - 1 1 JUNE 1982 JOINTLY ORGANIZED BY IAEA AND FAO l^J I N T E R ...»

-- [ Page 24 ] --

Nutrient agent, e f Ethylene propylene co-polymer.

ized products. Application o f this technology to agricultural usage has been slow, although discovery o f the porosigen-type system using thermoplastic matrices should see increasing technology transfer from the public health domain to agronomy and agriculture.

The special advantages, well discussed in a rapidly growing volume o f scientific literature, lie basically in extension o f the between-application interval, thus providing significant e c o n o m y o f labour. In agriculture this may be o f considerable value as regards trace nutrients and soil insecticides. Controlled release herbicides lasting beyond one growing season may be undesirable, especially where crop rotation is c o m m o n l y practised. In general, less chemical agent is required than that necessary in the conventional art. Reductions to 10% or less o f the agent quantity will give equivalent results, at least with the materials currently c o m mercialized. The luxurious consumption seen early in the herbicide and fertilizer treatment cycle is avoided. Environmental contamination is significantly decreased.

CARDARELLI and CARDARELLI

–  –  –

Moderate molecular weight carboxylated polyacrylate, manufactured by the a B.F. Goodrich Co.

k High molecular weight carboxylated polyacrylate.

Water soluble carboxylated polyacrylate.

^ Low molecular weight carboxylated polyacrylate, which provides tackiness to the developed envelope.

Adhesion promoter.

e ^ Source of divalent calcium ion for cross-linking.

® Maintains alkaline pH to prevent premature cross-linking.

Solvent.

h Preservative.

Once the agent is bound within a thermoplastic dispenser, such as a granule or pellet, it is not available in quantity to man or other non-target organisms. The health hazard exposure to agricultural workers has been dramatically reduced.

For instance, controlled release tributyltin fluoride, a molluscicide, shows no acute rodent toxicity compared with around 200 mg/kg rat LD 5 0 for the nonformulated powder.

Thermoplastics are inert and non-toxic. Once in the environment chemical degradation, generally to water, carbon dioxide and lower alkyls, proceeds extremely slowly and should have a reasonably negligible impact.

Thermoplastics are produced from petroleum or natural gas stocks and thus shortages can be predicted. However, current work indicates that controlled 242 CARDARELLI and CARDARELLI release agricultural chemical formulations can be made, using cellulosics and other products from renewable natural resources. The binding matrix element is relatively unimportant as long as free volume constraints to agent movement are overcome through proper compounding. The vital element is selection of the appropriate porosigen or porosigen mixes.

Controlled release granules, pellets or other geometrical dispenser forms lend themselves readily to the scientific study o f agent movement. Once inserted into the soil, for instance, the dispenser is relatively stationary, being water insoluble and t o o large for movement within the soil. Thus, the site o f agent injection is focal and agent transport through the surrounding soil is readily measurable. Through using radiolabeled herbicides, insecticides, etc. it is possible to analyse reliably soil, or plant, aliquots at a known distance from the dispenser and thus compute transport parameters and a time profile o f agent movement. Conventional agricultural chemical application does not readily allow such studies in that n o stable and stationary injection foci exist. Obviously the total amount released can be calculated by retrieval and analysis o f dispenser residues.

The authors have not studied radiolabeled agricultural agents in this regard but have, to date, confined their studies to 14 C-labelled and 113 Sn-labelled molluscicidal tin compounds. However, the above method o f determining agent movement is workable in both soil and water organotin transport studies.

–  –  –

[l ] FOLCKEMER, F.B., HANSON, R.E., MILLER, A., Resin compositions comprising organophosphorus pesticides, US Patent 3,318,769, May 9, 1967.

[2] MENN, J.J., FOLCKEMER, F.B., MILLER, A., Antihelmintic compositions and methods of employing same, US Patent 3,166,472, January 19, 1965.

[3] PASARELA, N.R., Acaricidal resin composition containing spiro [cyclopropane-1, -l'indene]-2-carboxylic acid, 3,3-dimethyl-a-cyano-M-phenoxybenzyl ester, US Patent 4,145,409, March 20, 1979.

[4] CARDARELLI, N.F., Controlled Release Pesticide Formulations, CRC Press, Boca Raton (1976).

[5] PRICE, M.D., Insecticidal resins — a new concept in residual insect control, Pest Control (1960) 47.

[6] FEINBERG, I., Process for preparing a stable polymer latex containing an insecticide, US Patent 3,400,093, September 3, 1968.

[7] KLEINBERGER, J., HERMAN, M., Insecticide, French Patent 1,568,198, April 14, 1969.

[8] HACKNEY, R.J., Insect resistant thermoplastic compositions, US Patent 3,408,323, March 13, 1968.

[9] ALLEN, G.G., Controlled release pesticides, Canadian Patent 846785, July 14, 1970.

[10] GREENBERG, J., CLOYD, G.D., Pet collar, US Patent 4,158,051, June 12, 1979.

[11] KYDONIEUS, A.F., SMITH, I.K., Efficacy of Hereon™ Polymeric Controlled Release Dispensers in Cockroach Control, Report Herculite Protective Fabrics Corp., New York (1974).





IAEA-SM-263/38 243 [12] HYMAN, S., BERNSTEIN, B.S., KAPOOR, R., Activated polymer materials and processes for making same, US Patent 3,705,938, December 12, 1972.

[13] HYMAN, S„ Bacteriostatic material, US Patent 3,279,986, October 19, 1966.

[14] CARDARELLI, N.F., NEFF, H.F., Compositions de préservation les incrustations sousmarines, French Patent 1506704, December 19, 1966.

[ 15] JANES, G.A., SENDERLING, R.L., "The diffusion-dissolution controlled release mechanism — performance evaluation of an antifouling coating after ten years service," Controlled Release (Proc. Int. Symp. New Orleans, 1979) Vol.11 (GOOD, M., BAKER, R., Eds) (1979) 3.

[16] CARDARELLI, N.F., Method for dispersing toxicants to kill disease spreading waterspawned larvae, trematodes, molluscs and similar organisms, and the products used in such methods, US Patent 3417181, December 17, 1968.

[17] CARDARELLI, N.F., CAPRETTE, S.J., Antifouling coverings, US Patent 3426473, February 11, 1969.

[ 18] CARDARELLI, N.F., NEFF, H.F., Biocidal elastomeric compositions, US Patent 3639583, February 1, 1972.

[19] CARDARELLI, N.F., Floating larvicide, US Patent 3590119, June 29, 1971.

[20] CARDARELLI, N.F., Rubber erases health hazards, Rubber World 166 (1972) 27.

[21] CARDARELLI, N.F., Slow release herbicides, Weeds, Trees and Turf (1972) 16, 36.

[22] CARDARELLI, N.F., Method of controlling the gastropod vectors of parasitic flukes, US Patent 3767809, October 23, 1973.

[23] CARDARELLI, N.F., MAJOR, C., Biocidal Rubber for Water Reclamation Systems, Air Force Systems Command, Report AMRL-TR-69-17, Wright-Patterson AFB, Dayton (1969).

[24] CARDARELLI, N.F., WALKER, K.E., Slow release copper toxicant compositions, US Patent 4012221, March 15, 1977.

[25] CARDARELLI, N.F., "The efficacy, environmental impact and mechanism of release and dispersal of pesticidal materials emitted from a controlled release polymeric dispenser", Advances in Pesticide Science, Vol.3 (GEISSBUHLER, H., Ed.), Pergamon Press (1979) 744.

[26] CARDARELLI, N.F., "Monolithic elastomeric materials", and ROSEMAN, T.J., CARDARELLI, N.F., "Monolithic polymeric devices", Controlled Release Technologies: Methods, Theory and Applications Vol.1. (KYDONIEUS, A.F., Ed.), CRC Press, Boca Raton ( 1980).

[27] CARDARELLI, N.F., Method and composition for the long term controlled release of a non-persistent organotin pesticide from an inert monolithic thermoplastic material, US Patent 4,116,111, August 28, 1979.

[28] CARDARELLI, N.F., Floating pesticide dispenser, US Patent 4228614, October 21, 1980.

[29] CARDARELLI, N.F., Method and composition for the long term controlled release of a non-persistent organotin pesticide from an inert monolithic thermoplastic dispenser, US Patent 423714, December 2, 1980.

[30] CARDARELLI, N.F., Biologically active insecticide containing polymeric formulation, US Patent 4237113, December 2, 1980.

[31] LAWS, E.R., et al., Field study of the safety of abate for treating potable water and observations on the effectiveness of a control programme involving both abate and malathion, Bull. World Health Organ. 38 (1968) 439.

[32] CARDARELLI, N.F., Controlled release molluscicides, Monograph, University of Akron (1977).

[33] CARDARELLI, N.F., EVANS, W.H., "Chemodynamics and environmental toxicology of controlled release organotin molluscicides", Controlled Release of Bioactive Materials, (BAKER, R., Ed.), Academic Press, New York (1980) 357.

CARDARELLI and CARDARELLI [34] CARDARELLI, N.F., Controlled release organotins as mosquito larvicides, Mosq. News 3 8 ( 1 9 7 8 ) 328.

[35] HIMEL, R., QUICK, T., BOSWELL, L., CARDARELLI, N.F., Field Evaluation of Controlled Release Mosquito Larvicide Dispensers, Report of the American Mosquito Association, Salt Lake City (1980) 13.

[36] THOMPSON, W.E., "Field tests of slow release herbicides", Controlled Release Pesticides (Proc. Symp. Akron, 1974), University of Akron, Akron (1974).

[37] HABER, F., "Die Geschichte des Gaskrieges," Fiinf Vortrage aus den Jahren 1 9 2 0 - 1 9 2 3, Springer Verlag, Berlin (1924) 76.

[38] QUINN, S.A., CARDARELLI, N.F., GANGSTAD, E.O., Aquatic herbicide chronicity, J. Aquat. Plant Manage. 15 (1977) 74.

[39] JANES, G.A., CARDARELLI, N.F., Aquatic Herbicides Chronicity Study, Office of the Chief Engineer, Department of the Army, Washington DC, Final Report DACW 73-73-C-0042 (1974).

[40] CARDARELLI, N.F., Controlled release aquatic herbicides, Weeds, Trees, and Turf 11 5 (1972).

[41] CARDARELLI, N.F., Controlled Release Aquatic Herbicides, Summary Rep., Acq. Réf., 1560-7-366, US Department of the Interior, Bureau Reclamation, Denver (1977).

[42] CARDARELLI, N.F., RADICK, C.M., Chronic Versus Acute Intoxication, Springer Verlag, Berlin (1982).

[43] CARDARELLI, N.F., BOSWELL, L., QUICK, T., "Efficacy of controlled release aquatic and terrestrial herbicides emitted from a thermoplastic dispenser", Controlled Release (Proc. Symp. Fort Lauderdale) 250.

[44] CARDARELLI, N.F., Controlled release herbicides, US Patent, approved for issue in 1982.

[45] CARDARELLI, N.F., Controlled release of trace nutrients, US Patent 4299613, Nov. 10, 1981.

[46] CARDARELLI, N.F., HIMEL, C„ NEIL, D., HOWITT, A., HOGMIRE, H., "Inflight Encapsulation of Insecticides", Controlled Release Bioactive Materials (Proc. Symp.

Gaithersburg, 1978), National Bureau of Standards, Gaithersburg (1978) 2.50.

[47] HIMEL, C.M., CARDARELLI, N.F., In-flight encapsulation of particles, US Patent 4286020, August 25, 1981.

Poster Presentations IAEA-SM-263/16

–  –  –

M. BOLAÑOS DE M O R E N O *, J. MOLINEROS* *Departamento de Plaguicidas, Ministerio de Agricultura y Ganadería * Departamento de Investigaciones, Comisión Ecuatoriana de Energía Atómica Quito, Ecuador

INTRODUCCION

Se analizaron residuos de BHC, Heptacloro y Aldrín en lechuga mediante cromatografía de gases.

MATERIALES Y METODOS

Aplicación de los insecticidas Los insecticidas fueron aplicados por aspersión foliar a plantas de lechuga de dos meses de edad, en las dosis indicadas en las recomendaciones técnicas de cada uno de los plaguicidas usados. Se efectuaron dos aplicaciones con una semana de intervalo.

Muestreo

• De las hojas se llevaron a cabo los siguientes muestreos:

1) Antes de la primera aplicación ( A - P l ) ;

2) Después de la primera aplicación (D-Pl );

3) Antes de la segunda aplicación (A-P2);

4) Después de la segunda aplicación (D-P2);

5) Una semana después de la última aplicación (1-S);

6) Dos semanas después de la última aplicación (2-S).

–  –  –

Análisis por cromatografía de gases Se extraen 30 gramos de muestra con una mezcla de hexano-acetona al 3:1, por licuado durante tres minutos. Dos particiones líquido-líquido con acetonitrilo preceden al "clean-up" por columna de Florisil, de la cual una mezcla de hexanoéter dietílico al 6,15 y 50% c o m o eluatos y una concentración previa a la inyección en cromatógrafo de gases con detector de captura de electrones de 63 Ni permiten cuantificar las concentraciones de plaguicidas en las muestras [1].

RESULTADOS Y CONCLUSIONES

Los resultados encontrados indican de una manera evidente lo que sucede con cada uno de los plaguicidas al ser aplicados en lechuga.

El BHC, dos semanas después de la última aplicación está a un nivel de 0,67 ppm, lo que está por bajo del límite máximo ( 2 ) [2].

El Heptacloro, dos semanas después de la última aplicación está a un nivel de 0,09 ppm, cifra que es superior al límite máximo (0,05 ppm).

El Aldrín, dos semanas después de la última aplicación está a un nivel de 0,14 ppm, frente al límite máximo que es 0,1 ppm.

Así, se puede concluir que si se siguen las recomendaciones de cada producto, y si se tiene muy en cuenta el límite de la última aplicación que se puede dar a un cultivo antes de la cosecha, se da tiempo a que el producto, si bien no desaparece completamente, por lo menos los residuos de plaguicidas estarán muy por debajo de los límites máximos y, por tanto, se podrán ofrecer alimentos libres de residuos tóxicos.

Tenemos proyectado continuar este trabajo comparando los resultados con los que se obtengan por ensayo radioinmunológico (RIA).

–  –  –

[1 ] BOLAÑOS DE MORENO, M., An assessment of the fungicide Vinclozolin with respect to strawberries, M. Sci. Thesis, Bristol University, 1976.

[2] Guía de límites máximos de residuos de plaguicidas del Codex, CAC/PR, enero de 1978.

POSTER PRESENTATIONS

IAEA-SM-263/5

ETUDE SUR LES RESIDUS

DE PRODUITS PHYTOSANITAIRES

DANS LES CULTURES DE TOMATES

ET DE PETITS POIS



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